CN101880431A - In-situ preparation method and application of nanometer molecular imprinting polymer membrane - Google Patents
In-situ preparation method and application of nanometer molecular imprinting polymer membrane Download PDFInfo
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- CN101880431A CN101880431A CN 201010211249 CN201010211249A CN101880431A CN 101880431 A CN101880431 A CN 101880431A CN 201010211249 CN201010211249 CN 201010211249 CN 201010211249 A CN201010211249 A CN 201010211249A CN 101880431 A CN101880431 A CN 101880431A
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Abstract
The invention discloses an in-situ preparation method of a nanometer molecular imprinting polymer membrane, which is characterized by comprising the following steps: (1) evenly mixing auxiliary membrane forming materials, functional monomers, template moleculars and an initiator in a proper solvent, and spinning on a smooth substrate by a spinning technology to form a composite membrane of a molecular imprinting polymer precursor; (2) obtaining a nano membrane by performing photo-initiation or thermal polymerization on the composite membrane of a molecular imprinting polymer precursor; and (3) eluting to remove the template moleculars in the nano membrane to obtain the molecular imprinting polymer membrane with a nanometer thickness. The method in the invention can introduce the proper auxiliary membrane forming materials into a molecular imprinting prepolymerization system, thus effectively improving the stability of the molecular imprinting membrane with a nanometer optical thickness prepared in an in-situ manner. Moreover, the substrate material used in the invention is not limited to conductive materials.
Description
Technical field
The invention belongs to sensing and separation technology field, be specifically related to a kind of in-situ preparation method and application in white light interference reflection spectrum sensing of nanometer molecular imprinting polymer membrane.
Background technology
Molecular imprinting (molecular imprinting) technology is one of technology comparatively popular in the prior art, its principle is can form the multiple action point when contacting with polymer monomer when template molecule (microsphere), will be memorized by this effect of polymerization process, after template molecule is removed, just formed the hole with multiple action point that is complementary with the template molecule sterie configuration in the polymkeric substance, such hole will have the selection evident characteristics to template molecule and analogue thereof.This technology all is widely used at aspects such as bionics, isolation technique, sensing technologies.Molecularly imprinted polymer material by the molecular imprinting preparation is molecular imprinting (molecular imprinting) material, it is a kind of polymer materials with simulation biomolecules recognition capability, not only the specific template molecule there are high affinity and selectivity, have simultaneously that the anti-adverse environment ability is strong, the advantage of good stability.
The molecularly imprinted polymer material adopts the in-situ polymerization under the mould qualification to prepare the imprinted polymer film owing to poorly soluble usually.The molecularly imprinted polymer particle of pre-preparation is disperseed with low boiling point solvent, then solution by dipping, drip and to be coated with or to be spun to substrate surface, though it is simple in the method that substrate surface forms molecular imprinted polymer membrane by solvent evaporates, the molecular imprinted polymer membrane thickness that adopts the preparation of this method generally micron dimension or more than, can be used for selective separation or preparation.Yet thickness is big because the film that film commonly used such as technology such as pressed film method, situ aggregation method and spin coating are made often exists, lack of homogeneity, circulation ratio and less stable, shortcoming such as be difficult to repeat, thereby greatly influenced the sensitivity of chemical sensor and the design typification of instrument, be difficult to use in the making of actual product.
Advantages such as the molecular imprinted polymer membrane of nanometer grade thickness has mass transfer apart from weak point, and adsorption process is fast are particularly suitable for the deielectric-coating of sensing technology.The molecular imprinted polymer membrane of preparation nano level optical thickness generally adopts the electropolymerization method in smooth substrate at present.After the electropolymerization method adopts and carry out the cyclic voltammetry scan certain hour in the solution of function monomer and template molecule, nanometer film is deposited on electrode surface, just can obtain remaining with the nanometer molecular imprinting polymer film in template molecule configuration hole behind the wash-out removal template molecule.The sub-trace transmitter of electropolymerization legal system back-up has some outstanding advantages, as prepares simply, carries out cyclic voltammetry scan and just can realize in the solution of function monomer and template molecule; And can on any conductive matrices, obtain the good ultrathin membrane of circulation ratio.But its weak point is selected substrate need be conductive substrates, and monomer must form polymkeric substance by the redox reaction of electrode simultaneously.But this defines the molecularly imprinted polymer material category that original position forms nano level optical thickness film to a great extent.The present invention comes therefrom.
Summary of the invention
The object of the invention is to provide a kind of in-situ preparation method of nanometer molecular imprinting polymer membrane, solved in the prior art molecular imprinting polymer membrane and could prepare by voltolisation is legal, the preparation condition strictness has limited the problems such as kind of molecular imprinting polymer membrane.
In order to solve these problems of the prior art, technical scheme provided by the invention is:
A kind of in-situ preparation method of nanometer molecular imprinting polymer membrane is characterized in that said method comprising the steps of:
(1) will assist film forming material, function monomer, template molecule and initiator in appropriate solvent, to mix, by the composite membrane of spin coating technique spin coating in smooth substrate formation molecularly imprinted polymer presoma;
(2) composite membrane by the molecularly imprinted polymer presoma carries out light-initiated or heat polymerization formation nanometer film;
(3) template molecule in the wash-out removal nanometer film promptly gets the molecular imprinting polymer membrane of nano thickness.
Preferably, described auxiliary film forming material is selected from polystyrene, polyvinyl alcohol; Described auxiliary film forming material in the concentration of mixture solution at 5mg/ml～100mg/ml.
Preferably, described function monomer is selected from N, N-diethylamide ethyl-methyl acrylate, vinylformic acid, methacrylic acid, trifluoromethyl acrylate, vinyl benzoic acid, methylene-succinic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 2-vinyl pyridine, 4-vinylpridine, vinyl imidazole, methyl methacrylate, hydroxyethyl methylacrylate, acrylamide, Methacrylamide a kind of.
Preferably, described solvent is selected from toluene, acetonitrile, chloroform, tetrahydrofuran (THF), normal hexane, ethanol, methyl alcohol etc.Preferably, described linking agent is selected from Ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, Vinylstyrene, trishydroxymethyl base propane trimethyl acrylic ester, pentaerythritol triacrylate, N, N '-methylene-bisacrylamide a kind of.
Preferably, described base material is selected from glass, silicon chip, golden film.
Preferably, the nanometer molecular imprinting polymer membrane optical thickness is in 50～1000nm.
The present invention also provides the described nanometer molecular imprinting polymer membrane of a kind of claim 1 in the application aspect the sensor information of white light interference reflection spectrum transmitter.
The in-situ preparing technology of molecular imprinting polymer membrane of the present invention, the auxiliary film forming material polystyrene of utilization etc. improves the stability of in-situ preparing molecular imprinting polymer membrane in the substrate.The optical thickness of described in-situ preparing molecular imprinting polymer membrane is controlled in nanometer range, can prepare the molecular imprinting polymer membrane of optical thickness in tens nanometers to 1 micron.Described in-situ preparing molecular imprinting polymer membrane has white light reflection interference spectrum (RIfS) sensing characteristics.
The used monomer of described molecular imprinting polymer membrane in-situ preparing is including but not limited to methacrylic acid, vinyl pyridine, conventional monomer such as acrylamide.Described original position molecular imprinting polymer membrane technology of preparing is meant earlier in smooth substrate, in the presence of auxiliary film forming material, utilize spin coating technique to prepare the composite membrane of molecularly imprinted polymer presoma, carry out molecularly imprinted polymer light-initiated or thermopolymerization formation nano thickness again.Described auxiliary film forming material includes but not limited to polystyrene, polyvinyl alcohol, and its film forming concentration is variable from 5mg/ml to 100mg/ml.Described base material is including but not limited to conventional materials such as glass, silicon chip, golden films.
The objective of the invention is to utilize spin coating technique film forming in substrate, polymerization process is limited in the thin film layer with this by the prepolymerization system of monomer, template molecule and initiator is mixed in appropriate solvent with auxiliary film forming material.Present method adds the stability that suitable auxiliary film forming material strengthens spin-coating film, and the optical thickness of controlling diaphragm is in the nano level scope simultaneously.Prepared molecular imprinted polymer membrane can be used as the deielectric-coating of transmitter.
The invention provides a kind of can be at the bottom of the nonconductive matrix technology of the molecular imprinting polymer membrane of in-situ preparing nanometer grade thickness.The present invention utilizes suitable auxiliary film forming material to mix in appropriate solvent with molecular imprinting polymeric monomer, template molecule and initiator, utilizes spin coating technique to form the molecule engram film of controllable thickness in selected substrate.Auxiliary film forming material has improved the viscosity and the polymerization environment of molecular imprinting prepolymerization system, has effectively improved film forming quality.Prepared molecular imprinting polymer membrane optical thickness is at nano level, and to the amount sensitivity of the template molecule of absorption.
With respect to scheme of the prior art, advantage of the present invention is:
The present invention introduces molecular imprinting prepolymerization system with suitable auxiliary film forming material, can improve the stability of in-situ preparing nano level optical thickness molecule engram film effectively.
Method proposed by the invention can be used for general molecular imprinting polymerization system, and common function monomer and template molecule all can utilize present method to prepare nano level optical thickness molecule engram film; Simultaneously, the used base material of present method also is not limited to electro-conductive material.The molecule engram film of the present invention's preparation can be used for the sensor information of transmitter.
In sum, the invention belongs to sensory field, be specifically related to a kind of in smooth substrate in-situ preparing be used for the method for the molecular imprinting polymer membrane of selective adsorption.Specifically, in the presence of auxiliary film forming material, the organic solution that includes function monomer, template molecule and initiator forms the prepolymerization film by spin coating technique in selected substrate, again illumination or heating certain hour in inert atmosphere.Zhi Bei molecular imprinting polymer membrane optical thickness can be as the sensitive membrane medium of white light interference reflection spectrum technology in nanometer range thus.
Description of drawings
Below in conjunction with drawings and Examples the present invention is further described:
Fig. 1 is Ta
2O
5The infrared spectrum of (b) behind (a) and the desorption before the paraxin blotting membrane desorption in the substrate;
Fig. 2 is Ta
2O
5The sem photograph of paraxin imprinted polymer film in the substrate;
Fig. 3 is repeatedly wash-out and the RIfS spectrum of absorption behind the template molecule of paraxin imprinted polymer film;
Fig. 4 is the infrared spectra of diethylstilbestrol imprinted polymer film;
Fig. 5 is the RIfS spectrum of diethylstilbestrol imprinted polymer film;
Fig. 6 is the variation of paraxin imprinted polymer optical thickness of thin film and the relation of chloromycetin solution concentration.
Embodiment
Below in conjunction with specific embodiment such scheme is described further.Should be understood that these embodiment are used to the present invention is described and are not limited to limit the scope of the invention.The implementation condition that adopts among the embodiment can be done further adjustment according to the condition of concrete producer, and not marked implementation condition is generally the condition in the normal experiment.
The preparation of embodiment 1 paraxin imprinted polymer film and optical property are measured
Molecularly imprinted polymer in the present embodiment is the paraxin imprinted polymer.Selected auxiliary film forming material is a polystyrene, and substrate is coated with the slide glass of tantalum pentoxide for the surface.Get 1ml 15mg/ml polystyrene toluene solution and 0.0646g paraxin, 0.08ml diethylamine ethyl-methyl acrylate, the 1ml ethylene glycol dimethacrylate mixes and adds after ultrasonic 10-60 minute the 0.02g Diisopropyl azodicarboxylate, the slide glass that is coated with tantalum pentoxide is placed on the sol evenning machine, film 2-20 second is got rid of with 100-1000 rev/min rotating speed by elder generation, get rid of film 20-200 second with 1000-6000 rev/min of rotating speed then, put into the vacuum drying oven of 40-80 degree afterwards, take out after 15-60 minute.
Fig. 1 is Ta
2O
5The infrared absorption spectra of (b) behind (a) and the desorption before the paraxin imprinted polymer film desorption in the substrate.Fig. 1 (a) is the not preceding infrared absorption spectra of desorption masterplate molecule of imprinted polymer film, and tangible paraxin characteristic group's absorption peak is arranged; Fig. 1 (b) is the infrared absorption spectra behind the imprinted polymer film desorption masterplate molecule, 1728.5cm
-1Be the charateristic avsorption band of the C=O of ester in the monomer, 967.8cm
-1Be the charateristic avsorption band of tertiary amine in the monomer, 3032cm
-1, 2926cm
-1, 1620cm
-1It is the charateristic avsorption band of polystyrene.The infrared formation that shows imprinted polymer.
Fig. 2 is Ta
2O
5The sem photograph of paraxin imprinted polymer film in the substrate shows relatively homogeneous of film surface.
Fig. 3 has shown the RIfS spectrum of prepared paraxin imprinted polymer film behind wash-out repeatedly and absorption template molecule, obtain the optical thickness (optical thickness=nd of paraxin imprinted polymer film behind wash-out and absorption template molecule thus, n is the specific refractory power of film, d is the physical thickness of film), list in table 1, wherein R
2For calculate the non-linear regression relation conefficient of optical thickness of thin film by RIfS spectrum.The optical thickness mean value that can draw three wash-out post polymerization thing films is 80.09nm, and standard deviation is 0.78nm, and relative standard deviation is 0.97%; The optical thickness mean value of twice absorption post polymerization thing film is 100.15nm, and the deviation of two times result is 1.17nm.Therefore, prepared paraxin imprinted polymer film is repeatedly showing very high stability behind wash-out and the adsorption experiment.
The optical thickness of table 1 paraxin imprinted polymer film behind wash-out and absorption template molecule
The preparation of embodiment 2 diethylstilbestrol imprinted polymer films and optical property are measured
Molecularly imprinted polymer in the present embodiment is the diethylstilbestrol imprinted polymer.Selected auxiliary film forming material is a polystyrene, and substrate is a silicon chip.Get 1ml 80mg/ml polystyrene toluene solution and 0.03g stilboestrol, 0.03g acrylamide, the 1ml ethylene glycol dimethacrylate mixes and adds after ultrasonic 10-60 minute the 0.02g Diisopropyl azodicarboxylate, silicon chip is placed on the sol evenning machine, film 2-20 second is got rid of with 100-1000 rev/min rotating speed by elder generation, get rid of film 20-200 second with 1000-6000 rev/min of rotating speed then, put into the vacuum drying oven of 40-80 degree afterwards, take out after 15-60 minute.
Fig. 4 is the infrared spectra of prepared diethylstilbestrol imprinted polymer film.1714.7cm
-1Be the charateristic avsorption band of C=O in the monomer, 1598.6cm
-1, 1486.6cm
-1Be the charateristic avsorption band of primary amine in the monomer, 3025cm
-1, 2921cm
-1It is the charateristic avsorption band of polystyrene.The formation of diethylstilbestrol imprinted polymer on the infrared demonstration silicon base.
Fig. 5 is the RIfS spectrum of the diethylstilbestrol imprinted polymer film of in-situ preparing on the silicon base, and calculating optics thickness of film by RIfS spectrum is 257nm.
The research of the preparation of embodiment 3 paraxin imprinted polymer films and film thickness and paraxin imprinted polymer concentration relationship
Molecularly imprinted polymer in the present embodiment is the paraxin imprinted polymer.Selected auxiliary film forming material is a polystyrene.Substrate is coated with the slide glass of tantalum pentoxide for the surface.Get 1ml 32mg/ml polystyrene toluene solution and 0.064g paraxin, 0.08ml diethylamine ethyl-methyl acrylate, the 1ml ethylene glycol dimethacrylate mixes and adds after ultrasonic 10-60 minute the 0.02g Diisopropyl azodicarboxylate, the slide glass that is coated with tantalum pentoxide is placed on the sol evenning machine, film 2-20 second is got rid of with 100-1000 rev/min rotating speed by elder generation, get rid of film 20-200 second with 1000-6000 rev/min of rotating speed then, put into the vacuum drying oven of 40-80 degree afterwards, take out after 15-60 minute.Behind the prepared paraxin imprinted polymer film desorption template molecule, its optical thickness change (optical thickness-absorption of Δ=absorption rear film preceding optics thickness of film) after the identical time of absorption in the chloromycetin solution of different concns.Fig. 6 is the changes delta of paraxin imprinted polymer optical thickness of thin film and the relation of chloromycetin solution concentration.As seen, the changes delta of paraxin imprinted polymer optical thickness of thin film and chloromycetin solution concentration present the favorable linearity variation relation.Obviously, prepared paraxin imprinted polymer film can be used as the deielectric-coating of RIfS transmitter.
Above-mentioned example only is explanation technical conceive of the present invention and characteristics, and its purpose is to allow the people who is familiar with this technology can understand content of the present invention and enforcement according to this, can not limit protection scope of the present invention with these embodiment.All equivalent transformations that spirit is done according to the present invention or modification all should be encompassed within protection scope of the present invention.
Claims (8)
1. the in-situ preparation method of a nanometer molecular imprinting polymer membrane is characterized in that said method comprising the steps of:
(1) will assist film forming material, function monomer, template molecule, linking agent and initiator in appropriate solvent, to mix, by the composite membrane of spin coating technique spin coating in smooth substrate formation molecularly imprinted polymer presoma;
(2) undertaken light-initiated by composite membrane or heat polymerization formation nanometer film to the molecularly imprinted polymer presoma;
(3) template molecule in the wash-out removal nanometer film promptly gets the molecular imprinting polymer membrane of nano thickness.
2. method according to claim 1 is characterized in that auxiliary film forming material is selected from polystyrene, polyvinyl alcohol in the described method; Described auxiliary film forming material in the concentration of mixture solution at 5mg/ml～100mg/ml.
3. method according to claim 1, it is characterized in that function monomer is selected from N in the described method, N-diethylamide ethyl-methyl acrylate, vinylformic acid, methacrylic acid, trifluoromethyl acrylate, vinyl benzoic acid, methylene-succinic acid, 2-acrylamide-2-methyl isophthalic acid-propanesulfonic acid, 2-vinyl pyridine, 4-vinylpridine, vinyl imidazole, methyl methacrylate, hydroxyethyl methylacrylate, acrylamide, Methacrylamide a kind of.
4. method according to claim 1 is characterized in that described solvent is selected from toluene, acetonitrile, chloroform, tetrahydrofuran (THF), normal hexane, ethanol, methyl alcohol.
5. method according to claim 1 is characterized in that base material is selected from glass, silicon chip, golden film in the described method.
6. method according to claim 1, it is characterized in that described linking agent is selected from Ethylene glycol dimethacrylate, ethylene glycol dimethacrylate, Vinylstyrene, trishydroxymethyl base propane trimethyl acrylic ester, pentaerythritol triacrylate, N, N '-methylene-bisacrylamide a kind of.
7. method according to claim 1 is characterized in that preparing the nanometer molecular imprinting polymer membrane optical thickness of gained in 50～1000nm.
8. the application of the described method of claim 1 aspect the sensor information film of preparation white light interference reflection spectrum transmitter.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688696A (en) * | 2012-05-25 | 2012-09-26 | 西安理工大学 | Method for preparing modified supported liquid membrane |
| CN105548151A (en) * | 2015-12-14 | 2016-05-04 | 江南大学 | Novel method for detection of codeine based on ionic iridium complex electrochemiluminescence and molecular imprinting recognition |
| CN107490576A (en) * | 2017-08-24 | 2017-12-19 | 北京化工大学 | A kind of photonic crystal hydrogel microsphere of quick detection agricultural chemicals, toxin and nano-particle and its preparation method and application |
| CN109540867A (en) * | 2018-11-30 | 2019-03-29 | 东南大学 | A kind of plasticiser Raman spectra detection process based on molecular engram nano fibrous membrane |
| CN109828017A (en) * | 2019-02-27 | 2019-05-31 | 昆明理工大学 | A kind of symetryne molecular imprinting electrochemical sensor and preparation method thereof |
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| US20030130462A1 (en) * | 1999-12-03 | 2003-07-10 | Mathias Ulbricht | Method for producing template-textured materials with high binding specificity and selectivity and utilization of said materials |
| CN101220167A (en) * | 2008-01-23 | 2008-07-16 | 清华大学 | Method for producing nano-stephanoporate intelligent photochemistry sensitization functional material |
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| US20030130462A1 (en) * | 1999-12-03 | 2003-07-10 | Mathias Ulbricht | Method for producing template-textured materials with high binding specificity and selectivity and utilization of said materials |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102688696A (en) * | 2012-05-25 | 2012-09-26 | 西安理工大学 | Method for preparing modified supported liquid membrane |
| CN102688696B (en) * | 2012-05-25 | 2015-02-18 | 西安理工大学 | Method for preparing modified supported liquid membrane |
| CN105548151A (en) * | 2015-12-14 | 2016-05-04 | 江南大学 | Novel method for detection of codeine based on ionic iridium complex electrochemiluminescence and molecular imprinting recognition |
| CN105548151B (en) * | 2015-12-14 | 2019-02-12 | 江南大学 | Based on ionic type iridium complex electrogenerated chemiluminescence-electropolymerization molecular engram recognition detection codeine novel method |
| CN107490576A (en) * | 2017-08-24 | 2017-12-19 | 北京化工大学 | A kind of photonic crystal hydrogel microsphere of quick detection agricultural chemicals, toxin and nano-particle and its preparation method and application |
| CN107490576B (en) * | 2017-08-24 | 2019-07-05 | 北京化工大学 | A kind of quick detection pesticide, toxin and photonic crystal hydrogel microsphere of nanoparticle and its preparation method and application |
| CN109540867A (en) * | 2018-11-30 | 2019-03-29 | 东南大学 | A kind of plasticiser Raman spectra detection process based on molecular engram nano fibrous membrane |
| CN109540867B (en) * | 2018-11-30 | 2021-07-27 | 东南大学 | Plasticizer Raman spectrum detection method based on molecularly imprinted nanofiber membrane |
| CN109828017A (en) * | 2019-02-27 | 2019-05-31 | 昆明理工大学 | A kind of symetryne molecular imprinting electrochemical sensor and preparation method thereof |
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Open date: 20101110 |