CN104945655A - Synthesis method and application of molecularly imprinted mesoporous material - Google Patents
Synthesis method and application of molecularly imprinted mesoporous material Download PDFInfo
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- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 3
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Abstract
The invention discloses a synthesis method of a molecularly imprinted mesoporous material. The method comprises the following steps: assembling an imprinted template molecule onto the surface of a mesoporous template in a solution, polymerizing an auto-polymerizable compound in the solution to form a mesoporous material, and finally, removing the template under acidic conditions to form the mesoporous ducts and imprinted cavities, thereby obtaining the molecularly imprinted mesoporous material. The method can efficiently and conveniently remove the template in the imprinted material; and all the obtained imprinted cavities are distributed on the internal surface of the mesoporous ducts, and thus, the molecularly imprinted mesoporous material has excellent accessibility. The obtained material has favorable selectivity and excellent antijamming ability for the target molecule when being used in complex biological samples. The double-template docking technique in the invention is also applicable to synthesis of other pore-system-based porous imprinted materials, and has wide application prospects in the field of functional materials and preparation and synthesis thereof.
Description
Technical field
The invention belongs to molecular imprinting functionalization Material Field, be specifically related to double-template docking structure, the preparation of oriented molecule engram technology and molecular imprinting mesoporous material and its in complex sample to the specific recognition of template molecule, abstraction and purification.
Background technology
Mesoporous material is the porous material [C.T.Kresge, M.E.Leonowicz, the W.J.Roth that lead a class of exploitation brand-new by the researcher Beck of Mobil company in the early 1990s, J.C.Vartuli, J.S.Beck, Nature (nature) 1992,359,710-712].Its duct arrangement high-sequential and aperture is homogeneous, simultaneously can continuously adjustabe from one dimension to three-dimensional on nanoscale, and has larger surface-area and pore volume.These characteristics make them in catalysis, sensing with the field such as to be separated and to have unrivaled superiority and wide application prospect.
Molecular imprinting [G.Wulff, A Sarhan, Angew.Chem.Int.Ed. (German applied chemistry) 1972,11,341-345; G.Vlatakis, L.I.Andersson, R.M ü ller, K.Mosbach, Nature (nature) 1993,361,645-647] be first template molecule and function monomer are formed title complex by a certain percentage, add linking agent again and form polymkeric substance thus fixed by template molecule and wrap up in the polymer, then adopt suitable method to be removed by template molecule, thus leave cavity and the optionally binding site of shape and template molecule complementation in the polymer.Molecular engram material has been widely used in the fields such as chromatographic separation, chemical sensitisation, medicament transport and bionic catalysis.So the combination of molecular engram material and mesoporous material, can by the highly selective of the unique advantage of bi-material as imprinted material, and the heavy body of mesoporous material and size exclusion effect etc. are brought into play, have very important application prospect simultaneously.
Although developed a series of molecular imprinting at present, as bulk trace [A.G.Strikovsky, D.Kasper, M.Grun, B.S.Green, J.Hradil, G.Wulff, J.Am.Chem.Soc. (American Chemical Society's proceedings) 2000, 122, 6295-6296], surface imprinted [M.Kempe, M.Glad, K.Mosbach, J.Mol.Recognit. (molecular recognition) 1995, 8, 35-39], directed trace [A.G.Guex, D.L.Birrer, G.Fortunato, H.T.Tevaearai, M.N.Giraud, Biomed.Mater. (biomedical material) 2013, 8, 2100-2101], boron imprinting [L.Li, Y.Lu, Z.J.Bie, H.Y.Chen, Z.Liu, Angew.Chem.Int.Ed. (German applied chemistry) 2013, 52, 7451-7454, J.Ye, Y.Chen, Z.Liu, Angew.Chem.Int.Ed. (German applied chemistry) 2014,53,10386-10389] etc.But these existing technology all cannot directly apply to the preparation of molecular imprinting mesoporous material.At present, the preparation method of molecular imprinting mesoporous material mainly contains three classes: 1) finish coat imprint surface [S.Dai afterwards, M.Burleigh, Y.Shin, C.Morrow, C.Barnes, Z.Xue, Angew.Chem.Int.Ed. (German applied chemistry) 1999, 38, 1235 – 1239], 2) based on surface imprinted pseudo-template imprinting [B.Johnson, B.Melde, P.Charles, D.Cardona, M.Dinderman, A.Malanoski, S.Qadri, Langmuir (Langmuir) 2008, 24, 9024 – 9029], 3) bulk covalency trace [J.E.Lofgreen, I.L.Moudrakovski, G.A.Ozin, ACS Nano (American Chemical Society-nanometer) 2011, 5, 2277-2287].But aforesaid method operation steps is all very loaded down with trivial details, some needs the special and compound that design and synthesis is new, and this all limits the application of these methods.
Summary of the invention
In order to overcome the complex steps preparing molecular imprinting mesoporous material method at present, the shortcomings such as suitability is limited, the object of the present invention is to provide a kind of general and synthetic method that is efficiently molecular imprinting mesoporous material.Present method not only efficiently can remove the template molecule in imprinted material easily, and thus the internal surface that the trace cavity obtained all is distributed in mesopore orbit has excellent accessibility.Final resulting materials is used for, in complex biological sample, having good selective enrichment ability for target molecule.
In order to achieve the above object, technical scheme of the present invention is as follows: a kind of synthetic method of molecular imprinting mesoporous material, the method be first by imprinted templates molecule by certain interaction force autonomous assembling mesoporous template surface in the solution, recycling the compound of auto-polymerization can be polymerized formation mesoporous material in the solution, the last template that removes in acid condition forms mesopore orbit and trace cavity, thus obtains molecular imprinting mesoporous material.
Aforesaid method is based on double-template docking and directed engram technology, and described double-template docking refers to that imprinted templates molecule is independently contained in the outside surface of rod-shaped micelle (mesoporous template) by certain interaction force and forms mixture.Described directed engram technology refers to imprinted templates and can combine by the functional group's boron affinity interaction in the compound of auto-polymerization.
Described mesoporous template is rod-shaped micelle, and described rod-shaped micelle is tensio-active agent; Described rod-shaped micelle is cationic surfactant, or aniorfic surfactant, or nonionic surface active agent.
Described cationic surfactant includes but not limited to cetyl trimethylammonium bromide, and described aniorfic surfactant includes but not limited to sodium lauryl sulphate.
Described imprinted templates molecule is AMP, or other produce the molecule of certain interaction force with mesoporous template.
Above-mentioned certain interaction force is electrostatic interactions.
Described can the compound (also known as pre-polymerization liquid) of auto-polymerization can be by tetraethoxy, APTES, the pre-polymerization liquid that the triethoxyl silane of amino-benzene boric acid modified is formulated also can be that other may be used for preparing the polymer monomer of mesoporous material; In described pre-polymerization liquid, tetraethoxy ratio is in the mixture 80% to 98%.
Described acidic conditions is acidic solution; Include but not limited to the methanol solution of hydrochloric acid, the compound method of the methanol solution of hydrochloric acid is: add in 150mL methyl alcohol 1.5mL mass concentration be 37.2% hydrochloric acid formulated.
When interaction force is electrostatic interactions, the concrete steps of aforesaid method are as follows:
First the electrostatic interactions between the micella molecule utilizing electronegative template molecule and positively charged, by the surface of microsphere assembling rod-shaped micelle in the solution, recycling containing can with the covalently bound functional group of template molecule the compound polymerization of auto-polymerization can form mesoporous material.Last wash-out microsphere (imprinted templates) and micella molecule (mesoporous template) in acid condition, thus in mesoporous material, form the three-dimensional trace cavity matched with imprinted templates shape of molecule.Due to the existence of double-template docking effect, the trace cavity that each template molecule is formed has good accessibility at mesopore surfaces, therefore has high template removal efficiency and an imprinting efficiency.Meanwhile, due to the employing of directed engram technology, the orientation of the trace cavity that each is formed by imprinted templates molecule keeps unified and controlled, which further improves the performance of gained imprinted material.
Above-mentioned based on double-template docking, the molecular imprinting mesoporous material of directed engram technology synthesis may be used at actual sample, the specific recognition to template molecule in especially in complex biological sample, abstraction and purification.
Beneficial effect: compared with prior art, the present invention proposes first based on double-template docking, with the immunoblot method of directed engram technology, has successfully prepared the mesoporous material of molecular imprinting.This technology is a kind of convenient, and efficient engram technology, not yet has similar document and patent report at present.Compared with conventional print technology (as bulk engram technology), present method is without the need to extra step but prepare resulting materials and have excellent performance, and especially its high imprinting efficiency [is better than the reported values in document.N.Sallacan, M.Zayats, T.Bourenko, A.B.Kharitonov, I.Willner, Anal.Chem. (analytical chemistry) 2002,74,702-712; A.Plewa, S.Yusa, M.Szuwarzynski, K.Szczubialka, Y.Morishima, M.Nowakowska, J.Med.Chem. (pharmaceutical chemistry) 2012,55,8712-8720.], and resulting materials shows outstanding specific recognition ability (compare in detail and see below subordinate list 1) for microsphere.Double-template docking technique in what is more important the present invention also goes in the synthesis based on the porous imprinted material of other pore systems, is with a wide range of applications at functional materials and preparation synthesis field.
Table 1 double-template docking-directed engram technology and bulk engram technology prepare the contrast of resulting materials performance
Accompanying drawing explanation
Fig. 1 is the schematic diagram of double-template docking-directed trace.
Fig. 2 is the synthetic route chart of the triethoxyl silane of amino-benzene boric acid modified.
Fig. 3 is the projection electron microscope photo of double-template docking-directed engram technology synthetic materials; Wherein scheming A is material monolithic shape appearance figure, and figure B is the enlarged view of single nanoparticle.
Fig. 4 is the X-ray powder diffraction figure of double-template docking-directed engram technology synthetic materials.
Fig. 5 is the nitrogen adsorption figure of double-template docking-directed engram technology synthetic materials; Wherein left figure is pore size distribution curve, and right figure is nitrogen adsorption curve.
Fig. 6 is double-template docking-directed engram technology synthetic materials for the crawl histogram of template molecule and structural similitude chaff interference thereof, and wherein A is double-template docking-directed engram technology synthetic materials, and B adopts bulk engram technology synthetic materials.The corresponding imprinted material of grey, the corresponding non-imprinted material of black.
Fig. 7 is Micellar Electrokinetic Chromatography (MEKC) figure of double-template docking-directed engram technology synthetic materials extraction human urine sample, wherein, a be centrifugal after human urine; B be centrifugal after human urine be used bulk engram technology synthetic materials extraction part; C be centrifugal after human urine be used the part of double-template docking-directed engram technology synthetic materials extraction; D is 0.1mg/mL standard adenosine sample; E is blank sample.
Embodiment
As shown in Figure 1, the synthetic method of a kind of molecular imprinting mesoporous material of the present invention, the method be first by imprinted templates molecule by certain interaction force autonomous assembling mesoporous template surface in the solution, recycling the compound of auto-polymerization can be polymerized formation mesoporous material in the solution, the last template that removes in acid condition forms mesopore orbit and trace cavity, thus obtains molecular imprinting mesoporous material.
Set forth the present invention further below by specific embodiment, should be noted that the following examples do not limit the present invention in any form, all employings are equal to replacement or the technical scheme that obtains of equivalent transformation mode, all drop within protection scope of the present invention.
Embodiment 1: the synthesis of the triethoxyl silane of amino-benzene boric acid modified
Synthesis step is see Fig. 2; be specially: in the round-bottomed flask of 25mL, add 10mmol glycidyl ether oxygen propyl triethoxy TMOS and 10mmol Resocinol-phenol formaldehyde resin; flask to be vacuumized and after being full of with nitrogen; inject 15mL tetrahydrofuran (THF), and then in nitrogen protection stirred at ambient temperature 12 hours.After boiling off solvent, obtain the solution S-1 of 1mmol/mL after gained oily liquids 10mL methyl alcohol dissolves again, i.e. the triethoxyl silane solution of amino-benzene boric acid modified.
Embodiment 2: the preparation of the thick product of molecular imprinting mesoporous material
First in 500mL round-bottomed flask, 0.6g cetyl trimethylammonium bromide is added, 168mg sodium hydroxide, 288mL water, obtain mixture, then, after said mixture being under agitation heated to 80 DEG C, adding 69.4mg AMP (AMP) and continue stirring and clarify to solution for 15 minutes.Then under violent stirring, in above-mentioned settled solution, drip pre-polymerization liquid, keep 80 DEG C to react after 2 hours, filter and obtain thick product.Above-mentioned pre-polymerization liquid is by 9.8mmol tetraethoxy, 0.2mmol APTES, and 0.2mmol solution S-1 mixes.
Above-mentioned anion surfactant cetyl trimethylammonium bromide can replace with the sodium lauryl sulphate (0.57g) of equimolar amount, and all the other steps remain unchanged.
Above-mentioned imprinted templates molecule AMP (AMP) can replace with the Guanosine 5'-Monophosphate of equimolar amount; The analog structure molecules such as monophosphate cytidine, all the other steps remain unchanged.
For the material synthesized based on bulk engram technology, microsphere is replaced with 53.4mg adenosine molecule, all the other steps remain unchanged.
For non-imprinted material, except not adding except microsphere, all the other steps remain unchanged.
Embodiment 3: the removal of template
In the present embodiment, the removal of template had both comprised the removal of mesoporous template, also comprised the removal of imprinted templates.The removal of above-mentioned two kinds of template molecules is simultaneously.Particularly, adopt the mode of surname extraction to remove template in acid condition, acidic conditions is acidic extraction liquid, and the hydrochloric acid that acidic extraction liquid is 37.2% by 1.5mL mass concentration is dissolved in the preparation of 150mL methanol solution and obtains, and extraction time is 24 hours.After extraction terminates, resulting materials vacuum-drying 12 hours at 60 DEG C; Namely described molecular imprinting mesoporous material is obtained.
Embodiment 4: the pattern of imprinted material and the sign of pore structure
The projection electron microscope of resulting materials, X-ray powder diffraction, nitrogen adsorption results of property is shown in Fig. 3 respectively, 4,5.Can prove that resulting materials has in a large number and the meso-hole structure of rule by above-mentioned several groups of data.
Embodiment 5: imprinted material is tested for the Grabbing properties of template molecule and chaff interference
First a series of tester solution is prepared, comprising two kinds of microspheres: adenosine and AMP, and a series of chaff interference: Desoxyadenosine; Guanosine; Cytidine; Guanosine 5'-Monophosphate; Monophosphate cytidine; UMP and dAMP, its concentration is all 1mg/mL, and solution used is the 50mM ammonium bicarbonate buffers (pH 8.5) containing 500mM sodium-chlor.Getting the molecular imprinting mesoporous material that 5mg prepares by embodiment 3 adds in the microsphere of the above-mentioned preparation of 900 μ L and the solution of chaff interference respectively, at room temperature vibrates 1 hour.Subsequently, 10, under the condition of 000 rev/min centrifugal 10 minutes, after removing supernatant liquor, with buffer solution three times, each 500 μ L, then added 50 μ L elutriants (elutriant is 100mM acetum), vibrate 1 hour.Finally, 10, under the condition of 000 rev/min centrifugal 10 minutes, take out elutriant, measure its absorbancy under 260nm, the size of its absorbancy can represent the amount of this molecular imprinting mesoporous material in conjunction with corresponding tester.
For the material synthesized based on bulk engram technology, and non-imprinted material test mode and above-mentioned steps just the same.
As shown in Figure 6: (1), compared to non-imprinted material, imprinted material all shows for the more excellent Grasping skill of imprinted templates molecule; (2) double-template docking-directed engram technology and bulk engram technology, two kinds of technology are compared, and the former resulting materials obviously shows for the more excellent recognition capability of template molecule.
Application examples 1: the selectivity that the material based on double-template docking-directed engram technology is used for adenosine in human urine captures and is separated
Human urine in the present embodiment takes from healthy male volunteers, is used in 10 before using, under the condition of 000 rev/min centrifugal 30 minutes, gets supernatant liquor and uses.Get 5mg material to add 500 μ L and contain in the 50mM ammonium bicarbonate buffers (pH 8.5) of 500mM sodium-chlor, after ultrasonic disperse, add 500 μ L urine supernatant liquors.Remain on 25 DEG C ± 2 DEG C vibrations 1 hour.Subsequently, 10, under the condition of 000 rev/min centrifugal 10 minutes, after removing supernatant liquor, with buffer solution three times, each 500 μ L, then added 50 μ L elutriants (elutriant is 100mM acetum), vibrate 1 hour.Finally, 10, under the condition of 000 rev/min centrifugal 10 minutes, take out elutriant, analyze for Micellar Electrokinetic Chromatography (MEKC).As seen from Figure 7, in extraction liquid based on bulk engram technology material, existing template molecule also has other chaff interferences, and significantly diminishes based on the amount of chaff interference in the extraction liquid of the material of double-template docking-directed engram technology and the peak intensity representing template molecule obviously increases.
Claims (10)
1. the synthetic method of a molecular imprinting mesoporous material, it is characterized in that, the method be first by imprinted templates molecule by certain interaction force autonomous assembling mesoporous template surface in the solution, recycling the compound of auto-polymerization can be polymerized formation mesoporous material in the solution, the last template that removes in acid condition forms mesopore orbit and trace cavity, thus obtains molecular imprinting mesoporous material.
2. according to claim 1 is a kind of synthetic method of molecular imprinting mesoporous material, and it is characterized in that, described mesoporous template is rod-shaped micelle, and described rod-shaped micelle is tensio-active agent.
3. according to claim 2 is a kind of synthetic method of molecular imprinting mesoporous material, and it is characterized in that, described rod-shaped micelle is cationic surfactant, or aniorfic surfactant, or nonionic surface active agent.
4. according to claim 1 is a kind of synthetic method of molecular imprinting mesoporous material, and it is characterized in that, described imprinted templates molecule is AMP, or other and mesoporous template produce the molecule of certain interaction force.
5. the synthetic method of a kind of molecular imprinting mesoporous material according to claim 1 or 4, is characterized in that, described certain interaction force is electrostatic interactions.
6. the synthetic method of a kind of molecular imprinting mesoporous material according to claim 1, it is characterized in that, described can the compound of auto-polymerization be by tetraethoxy, APTES, the pre-polymerization liquid that the triethoxyl silane of amino-benzene boric acid modified is formulated, or other can for the preparation of the polymerization single polymerization monomer of mesoporous material; In described pre-polymerization liquid, tetraethoxy ratio is in the mixture 80% to 98%.
7. the synthetic method of a kind of molecular imprinting mesoporous material according to claim 1, it is characterized in that, described acidic conditions is acidic solution.
8. the synthetic method of a kind of molecular imprinting mesoporous material according to claim 7, is characterized in that, described acidic solution is the methanol solution of hydrochloric acid, and compound method is: add in 150mL methyl alcohol 1.5mL mass concentration be 37.2% hydrochloric acid formulated.
9. the synthetic method of a kind of molecular imprinting mesoporous material according to claim 1, is characterized in that, described molecular imprinting mesoporous material in conjunction with imprinted templates molecule, and discharges combined imprinted templates molecule under the condition of pH >=7.0 under the condition of pH≤3.0.
10. the molecular imprinting mesoporous material made of the synthetic method of molecular imprinting mesoporous material according to claim 1 being separated, in enrichment and Industrial Catalysis in application.
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