CN101845127B - Method for preparing core-shell structured composite nano surface molecular imprinting polymer of tanshinone compound - Google Patents
Method for preparing core-shell structured composite nano surface molecular imprinting polymer of tanshinone compound Download PDFInfo
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Abstract
The invention relates to a method for preparing a core-shell structured composite nano surface molecular imprinting polymer of a tanshinone compound, which comprises preparation of a core monodisperse nano silicon dioxide particle. The method comprises the following preparation steps of: carrying out surface grafting modification on the prepared core monodisperse nano silicon dioxide particle, adding a template molecule and a functional monomer into 25mL of pore forming agent for mixing to prepare a preassembled solution and ultrasonically dispersing NanoSiO2-MTPU into the other 20mL of pore forming agent; then mixing the preassembled solution with the NanoSiO2-MTPU dispersed into the pore forming agent, adding a cross-linking agent and an initiating agent, stirring, importing nitrogen for removing oxygen and heating for triggering polymerization in the presence of the protection of the nitrogen; after the reaction is finished, centrifuging for removing supernatant, repeatedly and ultrasonically washing a product by a methanol-glacial acetic acid mixing solution till the template molecule can not be detected in the supernatant in an ultraviolet way; and then vacuum drying to constant weight and obtaining the core-shell structured composite nano surface molecular imprinting polymer of the tanshinone compound. The method can realize high selective separation, enrichment and detection on the tanshinone compound.
Description
One, technical field
The invention belongs to the molecularly imprinted polymer technical field, relate in particular to the preparation method who tanshinone compound is had the molecularly imprinted polymer of specific recognition.
Two, background technology
The red sage root is the dry root and rhizome of labiate red sage root Salva miltiorrhiza Bge., has the coronary artery dilating of highly significant, microcirculation improvement, and effects such as protection heart are one of clinical the most frequently used blood-activating and stasis-removing.At present, the red sage root and preparation thereof are sold and use as medicine or foodstuff additive in tens countries in the whole world, have obtained approval widely in the world wide.Since the thirties in 20th century, people have carried out number of research projects to chemical ingredients, the pharmacological action of red sage root single medicinal material and compound thereof, find that fat-soluble tanshinone compound is that the red sage root is antibiotic, anticancer, the active main efficient part of cardiovascular and cerebrovascular.43 tanshinone compounds from the red sage root, have been found at present, is wherein which composition its real effective constituent? behind the drug oral, most chemical ingredients can not be absorbed into blood by digestive tube, the composition that only enters blood just might become effective constituent, promptly contains real effective constituent in the serum.Therefore,, the existence form of tanshinone compound in serum analyzed, can fast and effeciently be found the drug action material that the red sage root is real by the serum drug chemical research.
The metabolism research of tanshinone compound in blood plasma, urine and ight soil at present has report, use methods such as LC-MS, GC-MS, HPCE-MS mostly, associated metabolic product to the red sage root in the pastille biological sample carries out qualitative analysis, and mainly be to analyze Tanshinone II A, the higher several tanshinone compounds of Cryptotanshinone equal size, some micro-meta-bolitess are often lost.In medicine internal metabolism research, not only to understand meta-bolites relevant information such as chemical structure, physico-chemical property accurately, and will enter relatively that the relative content of each component changes behind the blood, the biological activity of each component is judged and predicted.But, content is low, component is many because the activeconstituents in the serum has, separate difficult characteristics, and be subjected to the restriction of detection sensitivity, many real trace activity substances are not easy detected and separate, and can only carry out preliminary structure supposition work to the higher composition of some content.Therefore the serum drug chemical research of the red sage root presses for a kind of highly sensitive single-minded modern method for separating and detecting.
Recently, the development of molecular imprinting will most possibly provide powerful override and high efficiency selection for our mask work, molecularly imprinted polymer can either carry out enrichment to tanshinone compound in the red sage root administration serum, also can carry out separation and purification to the meta-bolites of different structure, realization is to the high efficiency separation and the detection of trace ingredients, thus some highly active micro-meta-bolitess in the discovery red sage root administration serum.One piece of isolating bibliographical information of TANSHINONES molecularly imprinted polymer [happy health, Fu Tingming, Guo Liwei are arranged at present.The West China pharmaceutical journal, 5 (2009) 443-445].But this molecularly imprinted polymer is the mode with mass polymerization to be prepared, a large amount of marking binding sites is in the inside of material, very difficulty of template molecules is removed wherein all in synthetic back, has 5% template molecule residual usually, and the affine efficient after the removal is also very low.And use the research that molecular imprinting comes the metabolism component of the separation detection red sage root in serum, do not appear in the newspapers as yet.
Three, summary of the invention
Goal of the invention:, the invention provides a kind of surface molecular imprinted polymer that tanshinone compound is had the specific recognition performance and preparation method thereof at the deficiency of present red sage root serum drug chemical research method and the shortcoming of traditional molecularly imprinted polymer self.Thereby realize highly selective separation, enrichment and detection to tanshinone compound.
Technical scheme: the preparation method of tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance, comprise the preparation of core monodisperse nano silicon dioxide particulate, preparation process is: the core monodisperse nano silicon dioxide particle that makes is carried out surface graft modification, described graft-modification method is: with core monodisperse nano silicon dioxide particle ultra-sonic dispersion in the volumetric concentration of MTPU is 15%～25% toluene solution, stir logical nitrogen deoxygenation down, stirring and refluxing 24h in 55 ℃ of environment makes NanoSiO then
2-MTPU uses toluene, methyl alcohol supersound washing, centrifugal more successively, removes unreacted MTPU, at last with prepared NanoSiO
2-MTPU is at 40 ℃ of following vacuum-drying 12h, and is standby; Template molecule, function monomer are added in the 25mL pore-creating agent and mix, fully shake up, place 4h down for 25 ℃, make pre-assembling solution, template molecule is the 0.1114g Tanshinone II A, and function monomer is a methacrylic acid, pore-creating agent is an acetonitrile, and the mol ratio of template molecule and function monomer is 1: 3～1: 4; With NanoSiO
2-MTPU ultra-sonic dispersion is in other 25mL pore-creating agent; Then with pre-assembled solution and the NanoSiO that is dispersed in the pore-creating agent
2-MTPU mixes, and adds linking agent and initiator, stirs logical nitrogen deoxygenation, under nitrogen protection, and the intensification initiated polymerization; Linking agent is an ethylene glycol dimethacrylate; Initiator is a Diisopropyl azodicarboxylate, and initiator amount is 5% of function monomer and a linking agent quality total amount, NanoSiO
2-MTPU particulate consumption is the corresponding 0.1114g template molecule of 0.1g, corresponding 50mL pore-creating agent; The mol ratio of template molecule and linking agent is 1: 5～1: 15; Reaction finishes the centrifugal supernatant liquor of removing in back, the product volume ratio is methyl alcohol-Glacial acetic acid mixing solutions supersound washing repeatedly of 9: 1, till the supernatant liquor ultraviolet detection is less than template molecule, vacuum-drying obtains tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance to constant weight then.
Core monodisperse nano silicon dioxide particulate preparation method is: strong aqua, positive tetraethyl orthosilicate and distilled water are added in the 100mL ethanol solution, make that strong aqua and alcoholic acid volume ratio are 0.01～0.40, positive tetraethyl orthosilicate and alcoholic acid volume ratio are 0.02～0.06, distilled water and alcoholic acid volume ratio are 0～0.04, rotating speed is 300～2000rpm, room temperature magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle.
Heating step during described intensification initiated polymerization is as follows: 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
Beneficial effect: one: with respect to prior art, patent of invention in 2006 (CN100999323A) discloses the preparation method who TNT is had the molecular imprinting silicon oxide nanoparticle of sensitive molecule identification.It adopts median size is the SiO of 100nm
2Particle is made carrier, at its finishing aminopropyl, and further amidation, make its surface have specific functional group.The present invention adopts MTPU as silane coupling agent, to nanometer SiO
2Particle carries out surface modification, thereby introduces amide molecule on nano silicon bead surface.The amide molecule on surface can be independently as function monomer directly and the Tanshinone II A combination, can be used as " bridge " again simultaneously, crosslinked with the EGDMA linking agent, formation core-shell structure inorganic-organic hybridization nanometer polymer.This method is simple to operate, productive rate height and favorable reproducibility.
Its two: the tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance that the present invention is prepared, compare with traditional molecularly imprinted polymer, the silica gel surface molecular imprinted polymer of preparation inorganic-organic hybridization, improved physical strength and the wearing quality of MIP, better application in stratographic analysis with separate.And preparation core-shell structure nano molecular imprinted polymer, make recognition site be based upon the polymer microballoon surface, reduced marking site by the phenomenon of " embedding ", marking molecular energy is very fast near recognition site, its association rate and separation efficiency are higher, can carry out selective separation and enrichment to tanshinone compound.
Four, description of drawings
Fig. 1 is the synthetic schemes of tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance among the present invention;
Fig. 2 is the sem photograph of synthetic core-shell structured composite nano surface molecular imprinting polymkeric substance of the present invention;
Fig. 3 is the transmission electron microscope picture of synthetic core-shell structured composite nano surface molecular imprinting polymkeric substance of the present invention;
Fig. 4 is the energy spectrogram of synthetic core-shell structured composite nano surface molecular imprinting polymkeric substance of the present invention; (A) NanoSiO
2The energy spectrogram; (B) CS-MIP can spectrogram.
Fig. 5 is synthetic core-shell structured composite nano surface molecular imprinting polymkeric substance of the present invention (A) Static Adsorption curve and (B) dynamic adsorption curve; ■ MIP; ● NIP.
Five, embodiment
The present invention will be further described below in conjunction with embodiment.
Positive tetraethyl orthosilicate (TEOS);
Core monodisperse nano silicon dioxide (NanoSiO
2);
O-(methacrylic acid oxygen ethyl)-N-(triethoxysilylpropyl) urethanum (MTPU);
Core-shell structure surface molecular imprinted polymer microballoon (CS-MIP);
Tanshinone II A (TSIIA);
Methacrylic acid (MAA);
Ethylene glycol dimethacrylate (EGDMA);
Diisopropyl azodicarboxylate (AIBN)
Under the room temperature 2.8mL strong aqua, 3.1mLTEOS and 1.3mL distilled water are added in the 100mL ethanol solution of high speed magnetic agitation fast, rotating speed is 500rpm, magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle.
Take by weighing the SiO that makes
2Particle 0.5g ultra-sonic dispersion adds the MTPU of 7.5mL in the 50mL toluene solution, logical N under the magnetic agitation
2Deoxygenation, rotating speed are 500rpm, and 55 ℃ of following stirring and refluxing 24h make NanoSiO
2-MTPU uses toluene, methyl alcohol supersound washing then, and is centrifugal, removes unreacted MTPU, at 40 ℃ of following vacuum-drying 12h, standby.
Delivery plate molecule 0.1114g, function monomer MAA0.09mL is dissolved in the 25mL acetonitrile solution, fully shakes up, and leaves standstill 4h under 25 ℃, and TSIIA molecule and MAA molecule are assembled in advance.Take by weighing the silica gel NanoSiO of 0.1g above-mentioned functionsization simultaneously
2-MTPU is dispersed in the acetonitrile solution of 25mL, ultrasonic 20min.Then with the solution and the dispersive NanoSiO of self-assembly
2-MTPU mixes, and adds linking agent EGDMA 0.6mL, initiator A IBN 31mg, logical N under the magnetic agitation
2Deoxygenation 15min, sealing, under nitrogen protection, the temperature programming initiated polymerization; 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
Reaction finishes the centrifugal supernatant liquor of removing in back, and product is with the supersound washing repeatedly of methyl alcohol-Glacial acetic acid (V/V, 9: 1) mixing solutions, till the supernatant liquor ultraviolet detection is less than template molecule.40 ℃ of vacuum-dryings obtain the molecularly imprinted polymer microballoon (CS-MIP) of core-shell structure, organic-inorganic hybridization to constant weight then.
The preparation process of non-imprinted polymer (CS-NIP), except that do not add template molecule in building-up process, all the other steps are identical with MIP.
Under the room temperature 12mL strong aqua, 3.6mL TEOS and 2.1mL distilled water are added in the 100mL ethanol solution of high speed magnetic agitation fast, rotating speed is 1500rpm, magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle.
Take by weighing the SiO that makes
2Particle 0.5g ultra-sonic dispersion adds the MTPU of 12.5mL in the 50mL toluene solution, logical nitrogen deoxygenation under the magnetic agitation, and rotating speed is 500rpm, 55 ℃ of following stirring and refluxing 24h make NanoSiO
2-MTPU uses toluene, methyl alcohol supersound washing then, and is centrifugal, removes unreacted MTPU, at 40 ℃ of following vacuum-drying 12h, standby.
Delivery plate molecule 0.1114g, function monomer MAA 0.11mL is dissolved in the 25mL acetonitrile solution, fully shakes up, and leaves standstill 4h under 25 ℃, and TSIIA molecule and MAA molecule are assembled in advance.Take by weighing the silica gel NanoSiO of 0.1g above-mentioned functionsization simultaneously
2-MTPU is dispersed in the acetonitrile solution of 25mL, ultrasonic 20min.Then with the solution and the dispersive NanoSiO of self-assembly
2-MTPU mixes, and adds linking agent EGDMA 1.1mL, initiator A IBN 61mg, and logical nitrogen deoxygenation 15min under the magnetic agitation, sealing, under nitrogen protection, the temperature programming initiated polymerization; 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
Reaction finishes the centrifugal supernatant liquor of removing in back, and product is with the supersound washing repeatedly of methyl alcohol-Glacial acetic acid (V/V, 9: 1) mixing solutions, till the supernatant liquor ultraviolet detection is less than template molecule.40 ℃ of vacuum-dryings obtain the molecularly imprinted polymer microballoon (CS-MIP) of core-shell structure, organic-inorganic hybridization to constant weight then.
The preparation process of non-imprinted polymer (CS-NIP), except that do not add template molecule in building-up process, all the other steps are identical with MIP.
Under the room temperature 4.1mL strong aqua, 3.8mL TEOS and 1.7mL distilled water are added in the 100mL ethanol solution of high speed magnetic agitation fast, rotating speed is 1000rpm, magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle.
Take by weighing the SiO that makes
2Particle 0.5g ultra-sonic dispersion adds the MTPU of 10mL in the 50mL toluene solution, logical nitrogen deoxygenation under the magnetic agitation, and rotating speed is 500rpm, 55 ℃ of following stirring and refluxing 24h make NanoSiO
2-MTPU uses toluene, methyl alcohol supersound washing then, and is centrifugal, removes unreacted MTPU, at 40 ℃ of following vacuum-drying 12h, standby.
Delivery plate molecule 0.1114g, function monomer MAA0.13mL is dissolved in the 25mL acetonitrile solution, fully shakes up, and leaves standstill 4h under 25 ℃, and TSIIA molecule and MAA molecule are assembled in advance.Take by weighing the silica gel NanoSiO of 0.1g above-mentioned functionsization simultaneously
2-MTPU is dispersed in the acetonitrile solution of 25mL, ultrasonic 20min.Then with the solution and the dispersive NanoSiO of self-assembly
2-MTPU mixes, and adds linking agent EGDMA 1.5mL, initiator A IBN 72mg, and logical nitrogen deoxygenation 15min under the magnetic agitation, sealing, under nitrogen protection, the temperature programming initiated polymerization; 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
Reaction finishes the centrifugal supernatant liquor of removing in back, and product methyl alcohol-Glacial acetic acid (V/V9: 1) mixing solutions supersound washing repeatedly, till the supernatant liquor ultraviolet detection is less than template molecule.40 ℃ of vacuum-dryings obtain the molecularly imprinted polymer microballoon (CS-MIP) of core-shell structure, organic-inorganic hybridization to constant weight then.
The preparation process of non-imprinted polymer (CS-NIP), except that do not add template molecule in building-up process, all the other steps are identical with MIP.
Embodiment 4
Under the room temperature 13.5mL strong aqua, 4.1mL TEOS are added in the 100mL ethanol solution of high speed magnetic agitation fast, rotating speed is 500rpm, magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle.
Take by weighing the SiO that makes
2Particle 0.5g ultra-sonic dispersion adds the MTPU of 10mL in the 50mL toluene solution, logical nitrogen deoxygenation under the magnetic agitation, and rotating speed is 500rpm, 55 ℃ of following stirring and refluxing 24h make NanoSiO
2-MTPU uses toluene, methyl alcohol supersound washing then, and is centrifugal, removes unreacted MTPU, at 40 ℃ of following vacuum-drying 12h, standby.
Delivery plate molecule 0.1114g, function monomer MAA0.12mL is dissolved in the 25mL acetonitrile solution, fully shakes up, and leaves standstill 4h under 25 ℃, and TSIIA molecule and MAA molecule are assembled in advance.Take by weighing the silica gel NanoSiO of 0.1g above-mentioned functionsization simultaneously
2-MTPU is dispersed in the acetonitrile solution of 25mL, ultrasonic 20min.Then with the solution and the dispersive NanoSiO of self-assembly
2-MTPU mixes, and adds linking agent EGDMA 1.2mL, initiator A IBN 64mg, and logical nitrogen deoxygenation 15min under the magnetic agitation, sealing, under nitrogen protection, the temperature programming initiated polymerization; 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
Reaction finishes the centrifugal supernatant liquor of removing in back, and product is with the supersound washing repeatedly of methyl alcohol-Glacial acetic acid (V/V, 9: 1) mixing solutions, till the supernatant liquor ultraviolet detection is less than template molecule.40 ℃ of vacuum-dryings obtain the molecularly imprinted polymer microballoon (CS-MIP) of core-shell structure, organic-inorganic hybridization to constant weight then.
The preparation process of non-imprinted polymer (CS-NIP), except that do not add template molecule in building-up process, all the other steps are identical with MIP.
Embodiment 5
Under the room temperature 31mL strong aqua, 2.3mL TEOS and 3.5mL distilled water are added in the 100mL ethanol solution of high speed magnetic agitation fast, rotating speed is 500rpm, magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle.
Take by weighing the SiO that makes
2Particle 0.5g ultra-sonic dispersion adds the MTPU of 9mL in the 50mL toluene solution, logical nitrogen deoxygenation under the magnetic agitation, and rotating speed is 500rpm, 55 ℃ of following stirring and refluxing 24h make NanoSiO
2-MTPU uses toluene, methyl alcohol supersound washing then, and is centrifugal, removes unreacted MTPU, at 40 ℃ of following vacuum-drying 12h, standby.
Delivery plate molecule 0.1114g, function monomer MAA0.09mL is dissolved in the 25mL acetonitrile solution, fully shakes up, and leaves standstill 4h under 25 ℃, and TSIIA molecule and MAA molecule are assembled in advance.Take by weighing the silica gel NanoSiO of 0.1g above-mentioned functionsization simultaneously
2-MTPU is dispersed in the acetonitrile solution of 25mL, ultrasonic 20min.Then with the solution and the dispersive NanoSiO of self-assembly
2-MTPU mixes, and adds linking agent EGDMA 1.5mL, initiator A IBN 68mg, and logical nitrogen deoxygenation 15min under the magnetic agitation, sealing, under nitrogen protection, the temperature programming initiated polymerization; 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
Reaction finishes the centrifugal supernatant liquor of removing in back, and product is with the supersound washing repeatedly of methyl alcohol-Glacial acetic acid (V/V, 9: 1) mixing solutions, till the supernatant liquor ultraviolet detection is less than template molecule.40 ℃ of vacuum-dryings obtain the molecularly imprinted polymer microballoon (CS-MIP) of core-shell structure, organic-inorganic hybridization to constant weight then.
The preparation process of non-imprinted polymer (CS-NIP), except that do not add template molecule in building-up process, all the other steps are identical with MIP.
Embodiment 6
Under the room temperature 26mL strong aqua, 5.7mL TEOS and 0.3mL distilled water are added in the 100mL ethanol solution of high speed magnetic agitation fast, rotating speed is 500rpm, magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle.
Take by weighing the SiO that makes
2Particle 0.5g ultra-sonic dispersion adds the MTPU of 10mL in the 50mL toluene solution, logical nitrogen deoxygenation under the magnetic agitation, and rotating speed is 500rpm, 55 ℃ of following stirring and refluxing 24h make NanoSiO
2-MTPU uses toluene, methyl alcohol supersound washing then, and is centrifugal, removes unreacted MTPU, at 40 ℃ of following vacuum-drying 12h, standby.
Delivery plate molecule 0.1114g, function monomer MAA0.12mL is dissolved in the 25mL acetonitrile solution, fully shakes up, and leaves standstill 4h under 25 ℃, and TSIIA molecule and MAA molecule are assembled in advance.Take by weighing the silica gel NanoSiO of 0.1g above-mentioned functionsization simultaneously
2-MTPU is dispersed in the acetonitrile solution of 25mL, ultrasonic 20min.Then with the solution and the dispersive NanoSiO of self-assembly
2-MTPU mixes, and adds linking agent EGDMA 1.3mL, initiator A IBN 65mg, and logical nitrogen deoxygenation 15min under the magnetic agitation, sealing, under nitrogen protection, the temperature programming initiated polymerization; 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
Reaction finishes the centrifugal supernatant liquor of removing in back, and product is with the supersound washing repeatedly of methyl alcohol-Glacial acetic acid (V/V, 9: 1) mixing solutions, till the supernatant liquor ultraviolet detection is less than template molecule.40 ℃ of vacuum-dryings obtain the molecularly imprinted polymer microballoon (CS-MIP) of core-shell structure, organic-inorganic hybridization to constant weight then.
The preparation process of non-imprinted polymer (CS-NIP), except that do not add template molecule in building-up process, all the other steps are identical with MIP.
The test implementation example
Test implementation example 1. scanning electron microscope and transmission electron microscope picture characterize
Fig. 2 is the sem photograph that the present invention has the core-shell structure molecularly imprinted polymer of recognition performance.As seen, the imprinted polymer spherolite degree of preparation is even, and monodispersity is good.
Fig. 3 is the energy spectrogram of core-shell structure molecularly imprinted polymer.(A) Yu (B) contrast as can be known, the present invention adopts MPTU as silane coupling agent, to NanoSiO
2Particle carries out surface modification, the success at NanoSiO
2Nitrogen and carbon molecule are introduced in the bead surface.This method is simple to operate, productive rate height and favorable reproducibility.
Fig. 4 is the transmission electron microscope picture of core-shell structure molecularly imprinted polymer.Particle diameter be 300nm modify the silica sphere preparation have the core-shell structure molecularly imprinted polymer of recognition performance, the thick about 12～23nm of the shell of polymkeric substance.(B) illustration on is the transmission photo of the nano-complex ball of amplification, and its shape characteristic is high-visible.
The test of test implementation example 2. Static Adsorption
Precision takes by weighing 14 parts of 20mg CS-MIP and CS-NIP, ultra-sonic dispersion is in the TSIIA acetonitrile solution of 0.25～2.5mmol/L in the 5mL series concentration respectively, airtight, room temperature jolting 30min, nylon membrane with 0.22 μ m after the adsorption equilibrium filters, TSIIA strength of solution before and after quantitatively dilution, ultraviolet-visible spectrophotometer are measured absorption in the 270nm place calculates equilibrium adsorption capacity Q according to formula (1)
e, parallel running three times.
The result is shown in Fig. 5 (A), and the adsorptive capacity of CS-MIP illustrates that much larger than CS-NIP CS-MIP is different from physical adsorption to the absorption of TSIIA, but a kind of selective adsorption that the specific recognition site is arranged.Because molecularly imprinted polymer is a Nano microsphere, and surface-area is big, its maximal absorptive capacity reaches 52.57 μ mol/g in addition.Be core simultaneously, improved physical strength and the wearing quality of CS-MIP, still can keep its more stable adsorptive capacity after reusing 10 times with silica gel.
Test implementation example 3. dynamic adsorption tests
Precision takes by weighing 14 parts of 20mg CS-MIP, ultra-sonic dispersion is in the TSIIA acetonitrile solution of 2mmol/L in 5mL concentration respectively, airtight, the room temperature jolting, nylon membrane 5,10,15,20,30,60, with 0.22 μ m behind the 90min filters respectively, TSIIA strength of solution before and after quantitatively dilution, ultraviolet-visible spectrophotometer are measured absorption in the 270nm place calculates equilibrium adsorption capacity Q according to formula (1)
e, parallel running three times.
The result is shown in Fig. 5 (B), and CS-MIP can reach adsorption equilibrium rapidly in 30min.This quick adsorptive power can be thought owing to preparation core-shell structure nano molecular imprinted polymer, make recognition site be based upon the polymer microballoon surface, reduced marking site by the phenomenon of " embedding ", marking molecular energy is very fast near recognition site, and its association rate and separation efficiency are higher.
Claims (3)
1. the preparation method of tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance, comprise the preparation of core monodisperse nano silicon dioxide particulate, described core monodisperse nano silicon dioxide particulate preparation method is: strong aqua, positive tetraethyl orthosilicate and distilled water are added in the 100mL ethanol solution, make that strong aqua and alcoholic acid volume ratio are 0.01～0.40, positive tetraethyl orthosilicate and alcoholic acid volume ratio are 0.02～0.06, distilled water and alcoholic acid volume ratio are 0～0.04, rotating speed is 300～2000rpm, room temperature magnetic agitation 24h; Supersound washing is to neutral, centrifugal repeatedly with dehydrated alcohol, and 40 ℃ of following vacuum-dryings make single NanoSiO of dispersion to constant weight
2Particle; It is characterized in that preparation process is:
A. the core monodisperse nano silicon dioxide particle that makes is carried out surface graft modification, described graft-modification method is: with core monodisperse nano silicon dioxide particle ultra-sonic dispersion in the volumetric concentration of MTPU is 15%～25% toluene solution, stir logical nitrogen deoxygenation down, stirring and refluxing 24h in 55 ℃ of environment makes NanoSiO then
2-MTPU uses toluene, methyl alcohol supersound washing, centrifugal more successively, removes unreacted MTPU, at last with prepared NanoSiO
2-MTPU is at 40 ℃ of following vacuum-drying 12h, and is standby;
B. template molecule, function monomer are added in the 25mL pore-creating agent and mix, fully shake up, place 4h down for 25 ℃, make pre-assembling solution, template molecule is the 0.1114g Tanshinone II A, function monomer is a methacrylic acid, and pore-creating agent is an acetonitrile, and the mol ratio of template molecule and function monomer is 1: 3～1: 4; With NanoSiO
2-MTPU ultra-sonic dispersion is in other 25mL pore-creating agent; Then with pre-assembled solution and the NanoSiO that is dispersed in the pore-creating agent
2-MTPU mixes, and adds linking agent and initiator, stirs logical nitrogen deoxygenation, under nitrogen protection, and the intensification initiated polymerization; Linking agent is an ethylene glycol dimethacrylate; Initiator is a Diisopropyl azodicarboxylate, and initiator amount is 5% of function monomer and a linking agent quality total amount, NanoSiO
2-MTPU particulate consumption is the corresponding 0.1114g template molecule of 0.1g, corresponding 50mL pore-creating agent; The mol ratio of template molecule and linking agent is 1: 5～1: 15;
C. reaction finishes the centrifugal supernatant liquor of removing in back, product methyl alcohol-Glacial acetic acid mixing solutions supersound washing repeatedly, till the supernatant liquor ultraviolet detection was less than template molecule, vacuum-drying obtained tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance to constant weight then.
2. the preparation method of tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance according to claim 1, heating step when it is characterized in that heating up initiated polymerization is as follows: 50 ℃ of reaction 6h, 60 ℃ of reaction 24h slowly are warmed up to 85 ℃ of reaction 6h at last.
3. the preparation method of tanshinone compound core-shell structured composite nano surface molecular imprinting polymkeric substance according to claim 1 is characterized in that methyl alcohol in methyl alcohol-Glacial acetic acid mixing solutions: the volume ratio of Glacial acetic acid is 9: 1.
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| CN102604008B (en) * | 2012-03-15 | 2014-07-09 | 江南大学 | Preparation method of pefloxacin surface molecular imprinting polymer and application thereof |
| CN102698721B (en) * | 2012-06-04 | 2014-04-09 | 江苏大学 | Preparation method for adsorbent for separating salicylic acid surface imprint from waste water |
| CN102775554B (en) * | 2012-07-06 | 2014-12-03 | 江南大学 | Preparation method for cinnamaldehyde surface molecularly imprinted polymer |
| CN103722802B (en) * | 2012-10-10 | 2016-01-06 | 中国科学院化学研究所 | With material and preparation method thereof under water environment with the transparency of nano silicon dioxide layer |
| CN103480350B (en) * | 2013-09-23 | 2015-05-20 | 哈尔滨工程大学 | Method for preparing molecularly imprinted polymer through silica gel surface coating |
| CN103570871B (en) * | 2013-10-21 | 2016-01-20 | 南京医科大学 | Mesoporous molecular sieve SBA-15 composite nano surface imprinted polymer and preparation method thereof |
| CN112552470B (en) * | 2020-10-21 | 2021-10-19 | 华南农业大学 | Teicoplanin-modified silica gel surface molecularly imprinted polymer, and aqueous phase preparation method and application thereof |
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| CN1715184A (en) * | 2004-06-28 | 2006-01-04 | 中国科学院理化技术研究所 | The preparation method of sphericity mesoporous silicon dioxide |
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