CN102964542A - RAFT (Reversible addition-fragmentation chain transfer) polymerization preparation method of magnetic mesoporous molecular imprinted hybrid silicon spheres - Google Patents
RAFT (Reversible addition-fragmentation chain transfer) polymerization preparation method of magnetic mesoporous molecular imprinted hybrid silicon spheres Download PDFInfo
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Abstract
The invention relates to a preparation method of magnetic mesoporous molecular imprinted hybrid silicon spheres. The preparation method comprises the following steps: firstly preparing Fe3O4 magnetic microspheres by adopting a solvothermal method, then coating mesoporous silica on the surfaces of the Fe3O4 magnetic microspheres through a sol-gel method and finally synthesizing the magnetic mesoporous molecular imprinted hybrid silicon spheres on the surfaces of the magnetic mesoporous silicon spheres by utilizing an RAFT (reversible addition-fragmentation chain transfer) molecular imprinting technology. The prepared magnetic mesoporous molecular imprinted hybrid silicon spheres can be used for selectively removing alkylphenol in drinking water. The preparation method disclosed by the invention has the advantages that the preparation method of the magnetic mesoporous molecular imprinted hybrid silicon spheres is reasonable in process and easy to implement; when the materials are used for removing alkylphenol type endocrine disruptors, the materials have good chemical stability and reusability and are easy to realize active adsorption, identification and separation against the alkylphenol; and according to the preparation method, the properties of magnetic mesoporous microspheres and a molecular imprinted polymer can be combined into a whole, the using efficiency of the molecular imprinting technology can be greatly improved and the range of molecular imprinting applications can be further expanded.
Description
[technical field]
The present invention relates to the preparation of molecular imprinting hybrid material, particularly a kind of RAFT polymerization process for preparing of magnetic mesoporous molecular imprinting hybrid silicon ball.
[background technology]
Since the nineties in 20th century, along with going from strength to strength and fast development of suitability for industrialized production, drinking water safety is subject to people's generally attention.In recent years, each large drinking water source of China all is subject to the pollution of trade effluent in various degree, and people's healthy and water-supply systems safety is all produced serious threat.At present, conventional Transformatin method and detection technique, can be used for control and detect organism and toxic substance, but for ubiquitous induced by alkyl hydroxybenzene endocrine disrupter in the trade effluent, conventional removal method and detection technique are all existing certain limitation in varying degrees.
Molecular imprinting is to grow up nearly decades, belongs to the high molecular polymer synthetic technology of supramolecular chemistry category.Its core is the molecularly imprinted polymer (Molecularly Imprinted Polymers, MIPs) that preparation has precordainment, identity and practicality.MIP is owing to have good, the characteristics such as identity is high, long service life, applied range of affinity, has been used in many research fields such as chemobionics sensor, chromatographic separation, Solid-Phase Extraction, membrane separation technique, antibody-be subjected to n-body simulation n.
RAFT (Reversible Addition-Fragmentation Chain Transfer, RAFT) polymerization is in traditional radical polymerization system, introduce a kind of chain transfer agents with dithioesters structure of high chain transfer constant, thus the activity of realization radical polymerization/controlled.The RAFT polymerization has the advantages such as practical monomer is in extensive range, reaction conditions is gentle, can carry out in traditional free radical polymerisation process, and can synthesize the high molecular polymer that block, star-like, pawl type etc. have special construction by molecular designing.In recent years, the RAFT aggregated application to the solid surface modification, had been enriched the Application Areas of RAFT polymerization.
Magnetic mesoporous silica-microsphere is owing to have high specific surface area, strong magnetic responsiveness, good biocompatibility, and microsphere surface can carry out surface-functionalized modification by means such as chemistry, physics.Magnetic mesoporous silica-microsphere not only has the characteristic of shell inorganic polymer, and the magnetic responsiveness of kernel can make under its outside magnetic field effect and separates rapidly from medium.Therefore, be widely used in the bioengineering fields such as target administration, cellular segregation, immobilized enzyme, biomedicine, immunology.In recent years magnetic mesoporous silica-microsphere is combined with the RAFT polymerization, at the functional polymer polymkeric substance of magnetic mesoporous silica-microsphere surface grafting nano-scale, further widened the Application Areas of magnetic polymer microsphere.
[summary of the invention]
The objective of the invention is to overcome tradition removes time-consuming in the induced by alkyl hydroxybenzene endocrine disrupter method, effort, removes the deficiencies such as efficient is low, a kind of RAFT polymerization process for preparing of magnetic mesoporous molecular imprinting hybrid silicon ball is provided, and is applied to the quick adsorption of induced by alkyl hydroxybenzene endocrine disrupter in the tap water and effectively removal.
Technical scheme of the present invention:
A kind of RAFT polymerization process for preparing of magnetic mesoporous molecular imprinting hybrid silicon ball at first adopts solvent thermal process to prepare Fe
3O
4Magnetic microsphere, then by sol-gel method at Fe
3O
4The coating mesoporous silicon-dioxide in magnetic microsphere surface obtains magnetic mesoporous silica-microsphere.Utilize at last the mesoporous molecular imprinting hybrid silicon of RAFT molecular imprinting synthesizing magnetic ball on the magnetic mesoporous silica-microsphere surface, comprise the steps:
1) Fe
3O
4The synthetic preparation of microballoon
Adopt the synthetic Fe of solvent-thermal method
3O
4Microballoon: with the FeCl of 1-3mmol
36H
2O is dissolved in the 20-50ml ethylene glycol, obtains yellow transparent solution.The 1-5mmol sodium acetate, anhydrous is joined in the mentioned solution, behind the magnetic agitation 30min, solution is changed in the 50-100ml stainless steel cauldron, put into baking oven at 180-220 ℃ of lower crystallization 8-72h.Product is washed 6 times with 30ml ethanol, and vacuum-drying obtains Fe
3O
4Microballoon.
2) preparation of magnetic mesoporous silica-microsphere
With the dried Fe of 0.1-0.3g
3O
4The microballoon ultra-sonic dispersion is to 50ml, and concentration is in the hydrochloric acid soln of 1-2mol/l, and ultra-sonic dispersion obtains water magnetic fluid solution after the magnetic resolution behind the ultra-sonic dispersion 10min, repeatable operation three times in the 20-60ml deionized water.Then with 2-5ml magnetic fluid ultra-sonic dispersion in 80ml dehydrated alcohol and 20ml deionized water, add 1-3ml ammoniacal liquor, ultra-sonic dispersion 10min, make it to disperse fully, under electric stirring, add 0.5-2mlTEOS, react 6-12h under the room temperature, the magnetic resolution product is used deionized water and absolute ethanol washing 3-5 time.Again with above-mentioned product ultra-sonic dispersion in the mixing solutions of the deionized water of 60-80ml and 0.3-0.5gCTAB, the ethanol that adds 1-2ml ammoniacal liquor and 60-80ml, after reacting 0.5h under the room temperature, the TEOS that adds 0.5-3ml, magnetic resolution product behind the reaction 6-12h, and behind water and the absolute ethanol washing 5 times extracts 24-48h with the magnetic mesoporous silica-microsphere after the washing repeatedly with the acetone of 60ml under 80 ℃, remove 60 ℃ of lower vacuum-drying 12h behind the CTAB, obtain magnetic mesoporous silica-microsphere.
3) preparation of the magnetic mesoporous silica-microsphere of RAFT reagent modification
Get magnetic mesoporous microballoon 0.1-0.3g, ultra-sonic dispersion is in the toluene of 50-80mL, and to the 4-that wherein adds 4-8mL (chloromethyl) phenyl-trichloro-silicane reagent, letting nitrogen in and deoxidizing 10min adds the triethylamine of 2-4mL, reacting by heating 12-24h.Magnet separated product after reaction finishes, product with toluene, ethanol and washing with acetone 3 times after, 60 ℃ of lower vacuum-dryings, obtain the magnetic mesoporous silica-microsphere that benzyl chloride is modified.
With the magnetic mesoporous silica-microsphere that the benzyl chloride of 0.5g-2g is modified, ultra-sonic dispersion is in the tetrahydrofuran solution of phenyl-magnesium-bromide of 5-8% in mass concentration, the 40-60 ℃ of lower dithiocarbonic anhydride that adds 2-8ml, reaction 24-72h.Reaction product is respectively washed 3 times with tetrahydrofuran (THF), anhydrous diethyl ether, ethanol successively.At 60 ℃ of lower vacuum-drying 24h, obtain the magnetic mesoporous silica-microsphere that RAFT reagent is modified.
4) the RAFT polymerization of magnetic mesoporous molecular imprinting hybrid silicon ball preparation
Magnetic mesoporous silica-microsphere, 45ml toluene, 1-4mmol alkylphenol, 6-10mmol acrylamide and the 20-40mmol Vinylstyrene of getting respectively the modification of 100-300mg RAFT reagent are put into there-necked flask and the sealing of 250ml, logical N behind the ultra-sonic dispersion
2Except O
210min, placing thermostat water bath to keep the system polymerization temperature is 50-70 ℃, injecting 5ml concentration in the enclosed system is 5mg/ml Diisopropyl azodicarboxylate acetonitrile solution, respectively wash three times with acetonitrile, ethanol behind the reaction 24h, then be 2: 8 glacial acetic acid and the mixing solutions of ethanol with the 200ml volume ratio, washing extraction alkylphenol can obtain target compound after the vacuum-drying.
A kind of application of prepared magnetic mesoporous molecular imprinting hybrid silicon ball, the selective removal that is used for the tap water alkylphenol, concrete grammar is: preparation pH is that 7 alkylphenol is drunk water sample, magnetic mesoporous molecular imprinting hybrid silicon ball is added vibration absorption in the water sample, in this process, carry out enrichment with external magnet, on the basis of considering temperature, adsorption time and concentration of substrate influence factor and repeating utilization factor, estimate imprinting efficiency and the clearance of this hybrid material.
Advantage of the present invention: the preparation method of magnetic mesoporous molecular imprinting hybrid silicon ball provided by the invention, technique is reasonable, easy to implement; The magnetic mesoporous molecular imprinting hybrid silicon ball of this law preparation is used for having good chemical stability, reusing when the induced by alkyl hydroxybenzene endocrine disrupter is removed, in magnetic field, has strong magnetic responsiveness, finish after " initiatively " of alkylphenol absorption and the identification at it, just can be separated at an easy rate adding under the action of a magnetic field, thereby reach initiative recognition and convenient purpose of separating; This preparation method integrates magnetic mesoporous microballoon and MIP characteristic, have strong magnetic responsiveness, precordainment, identity and practicality, to bring great convenience to the removal of induced by alkyl hydroxybenzene endocrine disrupter, and greatly improve the service efficiency of molecular imprinting, widen the scope that molecular imprinting is used.
[description of drawings]:
Fig. 1 is the Electronic Speculum figure of magnetic microsphere.
Fig. 2 is the Electronic Speculum figure of magnetic mesoporous silica-microsphere.
Fig. 3 is the Electronic Speculum figure of magnetic mesoporous silica-microsphere bisphenol A molecular engram hybrid silicon ball.
Fig. 4 is that magnetic mesoporous silica-microsphere bisphenol A molecular engram hybrid silicon ball separates photo with the adsorption time curve of non-trace hybrid silicon ball and the magnetic of molecular imprinting hybrid silicon ball.
[embodiment]:
Embodiment:
A kind of RAFT polymerization process for preparing of magnetic mesoporous molecular imprinting hybrid silicon ball at first adopts solvent thermal process to prepare Fe
3O
4Magnetic microsphere, then by sol-gel method at Fe
3O
4The coating mesoporous silicon-dioxide in magnetic microsphere surface obtains magnetic mesoporous silica-microsphere.Utilize at last the mesoporous molecular imprinting hybrid silicon of RAFT molecular imprinting synthesizing magnetic ball on the magnetic mesoporous silica-microsphere surface, comprise the steps:
1) Fe
3O
4The synthetic preparation of microballoon
Adopt the synthetic Fe of solvent-thermal method
3O
4Microballoon: with the FeCl of 1mmol
36H
2O is dissolved in the 40ml ethylene glycol, obtains yellow transparent solution.The 3mmol sodium acetate, anhydrous is joined in the mentioned solution, behind the magnetic agitation 30min, solution is changed in the 50ml stainless steel cauldron, put into baking oven at 200 ℃ of lower crystallization 24h.Product is washed 6 times with 30ml ethanol, and vacuum-drying obtains Fe
3O
4Microballoon.
Fig. 1 is the Electronic Speculum figure of magnetic microsphere, shows among the figure: Fe
3O
4Magnetic-particle is the globosity of rule, surface irregularity, and median size is about about 200nm.
2) preparation of magnetic mesoporous silica-microsphere
With the dried Fe of 0.2g
3O
4The microballoon ultra-sonic dispersion is to 50ml, and concentration is in the hydrochloric acid soln of 2mol/l, and ultra-sonic dispersion obtains water magnetic fluid solution after the magnetic resolution behind the ultra-sonic dispersion 10min, repeatable operation three times in the 50ml deionized water.Then with 3ml magnetic fluid ultra-sonic dispersion in 80ml dehydrated alcohol and 20ml deionized water, add 2ml ammoniacal liquor, ultra-sonic dispersion 10min, make it to disperse fully, under electric stirring, add 1mlTEOS, react 10h under the room temperature, the magnetic resolution product is used deionized water and absolute ethanol washing 4 times.Again with above-mentioned product ultra-sonic dispersion in the mixing solutions of the deionized water of 70ml and 0.4gCTAB, the ethanol that adds 2ml ammoniacal liquor and 80ml, after reacting 0.5h under the room temperature, the TEOS that adds 2ml, magnetic resolution product behind the reaction 12h, and behind water and the absolute ethanol washing 5 times extracts 48h with the magnetic mesoporous silica-microsphere after the washing repeatedly with the acetone of 60ml under 80 ℃, remove 60 ℃ of lower vacuum-drying 12h behind the CTAB, obtain magnetic mesoporous silica-microsphere.
Fig. 2 is the Electronic Speculum figure of magnetic mesoporous silica-microsphere, shows among the figure: Fe
3O
4Behind the microsphere surface coated silica, it is smooth that microsphere surface becomes, and microballoon size homogeneous, is uniformly dispersed, and median size is about about 400nm.
3) preparation of the magnetic mesoporous silica-microsphere of RAFT reagent modification
Get magnetic mesoporous microballoon 0.2g, ultra-sonic dispersion is in the toluene of 60mL, and to the 4-that wherein adds 5mL (chloromethyl) phenyl-trichloro-silicane reagent, letting nitrogen in and deoxidizing 10min adds the triethylamine of 3mL, reacting by heating 24h.Magnet separated product after reaction finishes, product with toluene, ethanol and washing with acetone 3 times after, 60 ℃ of lower vacuum-dryings, obtain the magnetic mesoporous silica-microsphere that benzyl chloride is modified.
With the magnetic mesoporous silica-microsphere that the benzyl chloride of 1g is modified, ultra-sonic dispersion is in the tetrahydrofuran solution of 7% phenyl-magnesium-bromide in mass concentration, 50 ℃ of lower dithiocarbonic anhydride that add 6ml, reaction 48h.Reaction product is respectively washed 3 times with tetrahydrofuran (THF), anhydrous diethyl ether, ethanol successively.At 60 ℃ of lower vacuum-drying 24h, obtain the magnetic mesoporous silica-microsphere that RAFT reagent is modified.
4) the RAFT polymerization of magnetic mesoporous molecular imprinting hybrid silicon ball preparation
Magnetic mesoporous silica-microsphere, 45ml toluene, 2mmol alkylphenol, 8mmol acrylamide and the 30mmol Vinylstyrene of getting respectively the modification of 200mg RAFT reagent are put into there-necked flask and the sealing of 250ml, logical N behind the ultra-sonic dispersion
2Except O
210min, placing thermostat water bath to keep the system polymerization temperature is 60 ℃, injecting 5ml concentration in the enclosed system is 5mg/ml Diisopropyl azodicarboxylate acetonitrile solution, respectively wash three times with acetonitrile, ethanol behind the reaction 24h, then be 2: 8 glacial acetic acid and the mixing solutions of ethanol with the 200ml volume ratio, washing extraction alkylphenol can obtain magnetic mesoporous bisphenol A molecular engram hybrid silicon ball after the vacuum-drying.
The preparation process of the non-trace hybrid silicon of magnetic mesoporous dihydroxyphenyl propane ball is the same, does not just add dihydroxyphenyl propane in reaction system.
Fig. 3 is the Electronic Speculum figure of magnetic mesoporous bisphenol A molecular engram hybrid silicon ball, shows among the figure: wrapped up one deck molecular engram film by RAFT polymerization preparation at magnetic mesoporous microsphere surface, thereby made the coarse unfairness that becomes of magnetic mesoporous silica-microsphere table.But because the controllable characteristics of RAFT polymerization, so that the molecular engram film of magnetic mesoporous silica-microsphere surface grafting is more even, the magnetic molecularly imprinted hybrid silicon ball of part slightly has adhesion phenomenon.
Prepared magnetic mesoporous bisphenol A molecular engram hybrid silicon ball is used for the selective removal of tap water alkylphenol, and take dihydroxyphenyl propane as target molecule, magnetic mesoporous bisphenol A molecular engram hybrid silicon ball and non-trace hybrid silicon ball are carried out the absorption property experiment to dihydroxyphenyl propane:
Compound concentration is 0.01-0.5mmol/L dihydroxyphenyl propane ethanolic soln, regulating pH is 7.0, get respectively the dihydroxyphenyl propane ethanolic soln 10ml of different concns, add magnetic mesoporous bisphenol A molecular engram hybrid silicon ball and non-each 20mg of trace hybrid silicon ball, shaking table vibration 10min, separate with external magnet, get respectively dihydroxyphenyl propane ethanolic soln before supernatant liquor and the absorption at 289nm place with its absorbance of mensuration under the ultraviolet spectrophotometer.Detected result shows: after magnetic mesoporous bisphenol A molecular engram hybrid silicon ball absorption, the absorbance of supernatant liquor dihydroxyphenyl propane ethanolic soln before the absorbance of 289nm adsorbs reduces greatly, less than 1/5th of the absorbance that adsorbs front dihydroxyphenyl propane ethanolic soln, magnetic mesoporous bisphenol A molecular engram hybrid silicon ball can reach 85% to the selective adsorption efficient of dihydroxyphenyl propane.
Be applied to the detection of dihydroxyphenyl propane in the tap water:
Method is the dihydroxyphenyl propane ethanolic soln with 10mL 2mol/L, is injected in the 100ml volumetric flask, adds pure water, obtains the actual water sample of dihydroxyphenyl propane.Get actual water sample 10mL, add each 20mg vibration absorption 20min of magnetic mesoporous bisphenol A molecular engram hybrid silicon ball and non-trace hybrid silicon ball, separate with external magnet, get respectively dihydroxyphenyl propane ethanolic soln before supernatant liquor and the absorption at 289nm place with its absorbance of mensuration under the ultraviolet spectrophotometer.Detected result shows: magnetic mesoporous bisphenol A molecular engram hybrid silicon ball can reach 68% to the selective adsorption efficient of dihydroxyphenyl propane in the actual water sample.
Fig. 4 is that magnetic mesoporous bisphenol A molecular engram hybrid silicon ball separates photo with adsorption time curve and the molecular imprinting hybrid silicon ball magnetic of non-trace hybrid silicon ball.Show among the figure: molecular imprinting hybrid silicon ball, adsorbs behind 15min and tends to balance gradually apparently higher than non-trace hybrid silicon ball the adsorption efficiency of dihydroxyphenyl propane.The magnetic property that magnetic mesoporous bisphenol A molecular engram hybrid silicon ball itself has can under the effect of externally-applied magnetic field, be separated from water sample rapidly.
Claims (2)
1. the preparation method of a magnetic mesoporous molecular imprinting hybrid silicon ball is characterized in that: at first adopt solvent thermal process to prepare Fe
3O
4Magnetic microsphere, then by sol-gel method at Fe
3O
4The coating mesoporous silicon-dioxide in magnetic microsphere surface obtains magnetic mesoporous silica-microsphere, utilizes at last the mesoporous molecular imprinting hybrid silicon of RAFT molecular imprinting synthesizing magnetic ball on the magnetic mesoporous silica-microsphere surface, comprises the steps:
1) Fe
3O
4The synthetic preparation of microballoon
Adopt the synthetic Fe of solvent-thermal method
3O
4Microballoon: with the FeCl of 1-3mmol
36H
2O is dissolved in the 20-50ml ethylene glycol, obtains yellow transparent solution; The 1-5mmol sodium acetate, anhydrous is joined in the mentioned solution, behind the magnetic agitation 30min, solution is changed in the 50-100ml stainless steel cauldron, put into baking oven at 180-220 ℃ of lower crystallization 8-72h; Product is washed 6 times with 30ml ethanol, and vacuum-drying obtains Fe
3O
4Microballoon;
2) preparation of magnetic mesoporous silica-microsphere
With the dried Fe of 0.1-0.3g
3O
4The microballoon ultra-sonic dispersion is to 50ml, and concentration is in the hydrochloric acid soln of 1-2mol/l, and ultra-sonic dispersion obtains water magnetic fluid solution after the magnetic resolution behind the ultra-sonic dispersion 10min, repeatable operation three times in the 20-60ml deionized water; Then with 2-5ml magnetic fluid ultra-sonic dispersion in 80ml dehydrated alcohol and 20ml deionized water, add 1-3ml ammoniacal liquor, ultra-sonic dispersion 10min, make it to disperse fully, under electric stirring, add 0.5-2mlTEOS, react 6-12h under the room temperature, the magnetic resolution product is used deionized water and absolute ethanol washing 3-5 time; Again with above-mentioned product ultra-sonic dispersion in the mixing solutions of the deionized water of 60-80ml and 0.3-0.5gCTAB, the ethanol that adds 1-2ml ammoniacal liquor and 60-80ml, after reacting 0.5h under the room temperature, the TEOS that adds 0.5-3ml, magnetic resolution product behind the reaction 6-12h, and behind water and the absolute ethanol washing 5 times extracts 24-48h with the magnetic mesoporous silica-microsphere after the washing repeatedly with the acetone of 60ml under 80 ℃, remove 60 ℃ of lower vacuum-drying 12h behind the CTAB, obtain magnetic mesoporous silica-microsphere;
3) preparation of the magnetic mesoporous silica-microsphere of RAFT reagent modification
Get magnetic mesoporous microballoon 0.1-0.3g, ultra-sonic dispersion is in the toluene of 50-80mL, and to the 4-that wherein adds 4-8mL (chloromethyl) phenyl-trichloro-silicane reagent, letting nitrogen in and deoxidizing 10min adds the triethylamine of 2-4mL, reacting by heating 12-24h; Magnet separated product after reaction finishes, product with toluene, ethanol and washing with acetone 3 times after, 60 ℃ of lower vacuum-dryings, obtain the magnetic mesoporous silica-microsphere that benzyl chloride is modified;
With the magnetic mesoporous silica-microsphere that the benzyl chloride of 0.5g-2g is modified, ultra-sonic dispersion is in the tetrahydrofuran solution of phenyl-magnesium-bromide of 5-8% in mass concentration, the 40-60 ℃ of lower dithiocarbonic anhydride that adds 2-8ml, reaction 24-72h; Reaction product is respectively washed 3 times with tetrahydrofuran (THF), anhydrous diethyl ether, ethanol successively; At 60 ℃ of lower vacuum-drying 24h, obtain the magnetic mesoporous silica-microsphere that RAFT reagent is modified;
4) the RAFT polymerization of magnetic mesoporous molecular imprinting hybrid silicon ball preparation
Magnetic mesoporous silica-microsphere, 45ml toluene, 1-4mmol alkylphenol, 6-10mmol acrylamide and the 20-40mmol Vinylstyrene of getting respectively the modification of 100-300mg RAFT reagent are put into there-necked flask and the sealing of 250ml, logical N behind the ultra-sonic dispersion
2Except O
210min, placing thermostat water bath to keep the system polymerization temperature is 50-70 ℃, injecting 5ml concentration in the enclosed system is 5mg/ml Diisopropyl azodicarboxylate acetonitrile solution, respectively wash three times with acetonitrile, ethanol behind the reaction 24h, then be 2: 8 glacial acetic acid and the mixing solutions of ethanol with the 200ml volume ratio, washing extraction alkylphenol can obtain target compound after the vacuum-drying.
2. application such as the prepared magnetic mesoporous molecular imprinting hybrid silicon ball of claim 1, it is characterized in that: the selective removal that is used for the tap water alkylphenol, concrete grammar is: preparation pH is that 7 alkylphenol is drunk water sample, magnetic mesoporous molecular imprinting hybrid silicon ball is added vibration absorption in the water sample, in this process, carry out enrichment with external magnet, on the basis of considering temperature, adsorption time and concentration of substrate influence factor and repeating utilization factor, estimate imprinting efficiency and the clearance of this hybrid material.
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