CN112920323B - beta-N-methylamino-L-alanine molecularly imprinted polymer - Google Patents

beta-N-methylamino-L-alanine molecularly imprinted polymer Download PDF

Info

Publication number
CN112920323B
CN112920323B CN202110336327.6A CN202110336327A CN112920323B CN 112920323 B CN112920323 B CN 112920323B CN 202110336327 A CN202110336327 A CN 202110336327A CN 112920323 B CN112920323 B CN 112920323B
Authority
CN
China
Prior art keywords
alanine
beta
methylamino
reaction
imprinted polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110336327.6A
Other languages
Chinese (zh)
Other versions
CN112920323A (en
Inventor
刘斌
华蕾
邵邱荣
包懿
王庆峰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Jilin Food Inspection Institute Jilin Food Production License Audit Center
Original Assignee
Jilin Food Inspection Institute Jilin Food Production License Audit Center
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Jilin Food Inspection Institute Jilin Food Production License Audit Center filed Critical Jilin Food Inspection Institute Jilin Food Production License Audit Center
Priority to CN202110336327.6A priority Critical patent/CN112920323B/en
Publication of CN112920323A publication Critical patent/CN112920323A/en
Application granted granted Critical
Publication of CN112920323B publication Critical patent/CN112920323B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/52—Amides or imides
    • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
    • C08F220/58—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide containing oxygen in addition to the carbonamido oxygen, e.g. N-methylolacrylamide, N-(meth)acryloylmorpholine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
    • C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
    • C08J2333/24—Homopolymers or copolymers of amides or imides

Abstract

The invention provides a beta-N-methylamino-L-alanine molecularly imprinted polymer, which belongs to the field of molecular imprinting detection and is prepared by mixing template molecules, functional monomers, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio and carrying out cross-linking polymerization; the functional monomers comprise N-acryloyl alanine, anthracene bridged quaternized vinyl imidazole and quaternized vinyl imidazolium salt; the molar ratio of the template molecule to the functional monomer is 1: (7-20); the molar ratio of N-acryloyl alanine, anthracene bridging quaternized vinyl imidazole and quaternized vinyl imidazolium salt in the functional monomer is (1-4): (0.1-3): (1-3); according to the invention, a 'template molecule-functional monomer' supramolecular complex is formed by a template molecule and a functional monomer in a pore-foaming agent through a special functional monomer, and then the molecularly imprinted polymer with good adsorption selectivity on beta-N-methylamino-L-alanine is prepared through cross-linking polymerization.

Description

beta-N-methylamino-L-alanine molecularly imprinted polymer
Technical Field
The invention relates to the technical field of molecular imprinting detection, in particular to a beta-N-methylamino-L-alanine molecular imprinting polymer.
Background
beta-N-methylamino-L-alanine (BMAA, beta-N-methylamino-L-alanine) is a neurotoxic L-nonprotein amino acid secreted by blue algae, the structure of the L-nonprotein amino acid is similar to that of lysine and alanine in 20 amino acids necessary for human body to synthesize protein, and the molecular formula is C 4 H 10 N 2 O 2 Relative to the molecular mass 118, the blue-green algae is easily soluble in water, can be released into a water environment through certain growth activities in the growth process of the blue-green algae, and is dissolved in the water environment; studies have shown that BMAA can damage motor neurons. In natural environment, BMAA can be transmitted along food chain, has biological amplification phenomenon, and can be involved in amyotrophic lateral sclerosis and Parkinson dementiaThe onset of the syndrome. Most of cyanobacteria plankton (blue algae) can produce BMAA, and the blue algae widely existing in the environment can pose a threat to human health.
Molecular imprinting is an emerging molecular recognition technology that has attracted much attention in recent years, and is a method for preparing a polymer having a specific "memory function" for a template by using a compound to be recognized as the template molecule (or an imprinting molecule or a target molecule). In the preparation process of the molecularly imprinted Polymer, firstly, template molecules and functional monomers form a host-guest compound in a solution system through intermolecular force, then, the host-guest compound is fixed in a highly crosslinked Polymer matrix through free radical polymerization reaction under the existence of a cross-linking agent through photo-initiation or thermal initiation, and the template molecules are washed away in a certain solvent to obtain a rigid Polymer (molecularly imprinted Polymer, MIP) with a cavity with a determined spatial configuration and accurately arranged functional groups in the cavity. MIP of a certain template molecule prepared by molecular imprinting technology has specific affinity to the template molecule, and the template molecule can be identified from molecules with similar structures. This particular recognition effect is formed by the following two aspects: firstly, removing template molecules, and leaving action cavities matched with the shapes of the template molecules on the polymer; secondly, the functional groups which originally interact with the template molecules are still remained at the original positions around the cavities, and in the subsequent re-identification process, the functional groups which are fixedly arranged can form an accurate complementary relationship with the target molecules, so that the cavities with the shape matching function form high selectivity and identification capability which are specific to the target molecules. The molecular imprinting can be used for separating and enriching target molecules in a complex sample, is a potential BMAA separation and enrichment method, and the prior art has no molecular imprinting material or molecular imprinting detection method aiming at beta-N-methylamino-L-alanine to realize the separation and detection of the beta-N-methylamino-L-alanine.
Disclosure of Invention
In view of the above problems, the present invention aims to provide a beta-N-methylamino-L-alanine molecularly imprinted polymer and a preparation method thereof; can overcome the complex pretreatment process of an environment or food sample system and provide convenience for the enrichment and separation of samples.
The purpose of the invention is realized by adopting the following technical scheme:
a beta-N-methylamino-L-alanine molecularly imprinted polymer is prepared by mixing template molecules, functional monomers, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, and performing cross-linking polymerization; wherein the content of the first and second substances,
the template molecule is beta-N-methylamino-L-alanine;
the functional monomers comprise N-acryloyl alanine, anthracene bridged quaternized vinyl imidazole and quaternized vinyl imidazolium salt;
the molar ratio of the template molecules to the functional monomers is 1: (7-20), wherein the molar ratio of the functional monomer to the cross-linking agent, the pore-foaming agent and the initiator is 1: (0.5-5): (20-45): (0.05-0.1);
the molar ratio of N-acryloyl alanine, anthracene bridging quaternized vinyl imidazole and quaternized vinyl imidazolium salt in the functional monomer is (1-4): (0.1-3): (1-3).
Preferably, the crosslinking agent is N, N '-methylenebisacrylamide, N' -1,4-phenylenediacrylamide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane trimethacrylate, 3,5-di (acrylamide) benzoic acid, or ethylene glycol dimethacrylate; the pore-foaming agent is one or two of dimethyl sulfoxide, isopropanol, acetone, dichloromethane, chloroform and carbon tetrachloride; the initiator is organic peroxide or azo compound.
The organic peroxide is dibenzoyl peroxide, cyclohexanone peroxide, methyl ethyl ketone peroxide, dibenzoylphthalin peroxide or a mixture thereof; the azo compound is azobisisobutyronitrile, azobisisoheptonitrile or a mixture thereof.
Preferably, the cross-linking agent is N, N' -methylenebisacrylamide or pentaerythritol tetraacrylate.
The invention also provides a preparation method of the beta-N-methylamino-L-alanine molecularly imprinted polymer, which comprises the following steps:
s1, weighing beta-N-methylamino-L-alanine, a functional monomer, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, firstly placing the beta-N-methylamino-L-alanine and the functional monomer into a reactor, adding the pore-forming agent, stirring until the beta-N-methylamino-L-alanine and the functional monomer are completely dissolved, standing for 4-10h, adding the cross-linking agent and the initiator, fully mixing and stirring uniformly, introducing nitrogen to remove oxygen, sealing a reaction system, replacing reaction atmosphere with nitrogen, and carrying out polymerization reaction under a thermal initiation or photo initiation condition to obtain a polymerization product;
s2, crushing and grinding the polymerization product, sieving the obtained product by using a 200-mesh sieve, sufficiently eluting the sieved polymerization product by using an eluent until no beta-N-methylamino-L-alanine is washed out, washing and then drying in vacuum to obtain the beta-N-methylamino-L-alanine molecularly imprinted polymer;
wherein the eluent is a mixed solution of methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is (6-10): 1.
preferably, the conditions of thermal initiation are: controlling the reaction temperature in a constant-temperature water bath at 60-80 ℃, and carrying out heat preservation reaction for 12-36h; the photoinitiated conditions were: reacting for 12-36h under a high-pressure mercury lamp.
Preferably, the preparation method of the anthracene-bridged quaternized vinyl imidazole comprises the following steps:
a1, accurately weighing 1 part of anthracene, 0.5 part of trioxymethylene, 0.02 part of hexadecyl trimethyl ammonium bromide and 1.5 parts of glacial acetic acid according to parts by weight, fully stirring and mixing, dropwise adding 5.2 parts of 47wt.% hydrobromic acid solution while stirring, continuously stirring for 1-20min after dropwise adding, heating to 70-80 ℃, keeping the temperature and stirring for reaction for 4-5h, cooling after the reaction is finished, filtering, washing precipitates with deionized water, drying, and recrystallizing with toluene to obtain a bromomethylation product;
a2, weighing 2 parts of bromomethylation product and 1.4 parts of vinyl imidazole, adding 52 parts of toluene, 52 parts of 10mol/L potassium hydroxide solution and 0.4 part of n-butyl alcohol, fully stirring and mixing, heating and refluxing for 10-12h, cooling after the reaction is finished, filtering, washing the filtrate with deionized water, drying an oil layer with anhydrous magnesium sulfate or anhydrous sodium sulfate, then evaporating the solvent under reduced pressure, and recrystallizing the chloroform-cyclohexane mixed solution with the same volume ratio to obtain anthracene-bridged imidazole;
and A3, weighing 2 parts of anthracene bridged imidazole, adding 20 parts of isopropanol, fully mixing and stirring uniformly, heating to 60-70 ℃, dropwise adding 0.9 part of bromopropylene, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction for 12-14h, cooling after the reaction is finished, steaming to remove the bromopropylene at normal pressure, steaming to remove the isopropanol at reduced pressure, recrystallizing the product from acetone-ethyl acetate mixed solution mixed in equal volume ratio, and drying to obtain the anthracene bridged imidazole.
Preferably, the preparation method of the quaternized vinyl imidazolium salt comprises the following steps:
according to a molar ratio (1-1.2): 1, weighing vinyl imidazole and bromoalkane, dissolving the vinyl imidazole and the bromoalkane in isopropanol, fully mixing and stirring uniformly, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction at 70-80 ℃ for 16-24h, and carrying out reduced pressure distillation to remove the isopropanol after the reaction is finished to obtain the quaternized vinyl imidazolium salt.
The invention also provides a surface molecularly imprinted polymer comprising the beta-N-methylamino-L-alanine molecularly imprinted polymer, which comprises an inert mesoporous microsphere carrier and a molecularly imprinted polymer covering the surface of the inert mesoporous microsphere carrier.
Preferably, the inert mesoporous microsphere carrier is silica gel, silicon dioxide, polyvinyl chloride, polystyrene or activated carbon.
Preferably, the preparation method of the beta-N-methylamino-L-alanine surface molecularly imprinted polymer comprises the following steps:
b1, adding the inert mesoporous carrier into a dilute acid solution for soaking and cleaning, washing the inert mesoporous carrier to be neutral by distilled water to obtain an activated mesoporous carrier, and performing surface modification on the activated mesoporous carrier by using a silane coupling agent to obtain a modified mesoporous carrier; wherein the concentration of hydrogen ions in the dilute acid solution is 0.1-2mol/L; the silane coupling agent is 4- (chloromethyl) phenyl trimethoxy silane, vinyl trimethoxy silane or gamma-methacryloxypropyl trimethoxy silane;
b2, weighing beta-N-methylamino-L-alanine, a functional monomer, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, firstly placing the beta-N-methylamino-L-alanine and the functional monomer into a reactor, adding the pore-forming agent, stirring until the beta-N-methylamino-L-alanine and the functional monomer are completely dissolved, standing for 4-10h, adding the cross-linking agent and the modified mesoporous carrier, uniformly mixing, adding the initiator, uniformly mixing and stirring, introducing nitrogen, removing oxygen, closing a reaction system, replacing reaction atmosphere with nitrogen, and carrying out polymerization reaction under a thermal initiation or photo initiation condition to obtain a surface imprinting product;
and B3, washing the surface imprinting product by using a pore-foaming agent, sufficiently eluting the surface imprinting product by using an eluent until no beta-N-methylamino-L-alanine is eluted, washing again, and then drying in vacuum to obtain the beta-N-methylamino-L-alanine surface molecularly imprinted polymer.
The invention has the beneficial effects that:
(1) The invention uses special functional monomer, beta-N-methylamino-L-alanine as template molecule, the template molecule and functional monomer form 'template molecule-functional monomer' supermolecule compound in pore-foaming agent through hydrogen bond, van der Waals force, electrostatic force, etc.; the molecularly imprinted polymer with good adsorption selectivity to beta-N-methylamino-L-alanine is prepared under the conditions of a cross-linking agent and an initiator, and particularly, the N-acryloyl alanine derivative with a structure similar to that of a template molecule is used as a monomer, and good affinity and selectivity with the template molecule are provided for the polymer based on good structure matching.
(2) BMAA has carboxyl, primary amino and secondary amino, is zwitter ion and is in a protonized ionized state in aqueous solution, anthracene bridging quaternized vinyl imidazole is used as a functional monomer, so that interaction including electrostatic force can be formed between template molecules and the monomer, and meanwhile, a rigid anthracene skeleton enables the structure of the polymer to have certain rigidity and mechanical stability, the spatial configuration of an imprinted cavity and the position of a complementary functional group are ensured, and the molecularly imprinted polymer can be applied under high pressure; meanwhile, the functional monomer is doped with quaternized vinyl imidazolium salt, and the spatial structure has certain flexibility so as to ensure that the affinity kinetics reach balance as soon as possible, and affinity sites are easy to access.
(3) According to the invention, an inert mesoporous microsphere carrier is used as a template, an imprinted polymer with a mesoporous structure is prepared on the mesoporous carrier, and the advantages of molecular imprinting specificity and mesoporous material high specific surface are combined, so that most of recognition sites in the polymer are located on the surface of the mesoporous microsphere carrier, and the imprinted polymer has higher adsorption capacity, faster mass transfer rate and stronger binding kinetics.
Drawings
The invention is further illustrated by means of the attached drawings, but the embodiments in the drawings do not constitute any limitation to the invention, and for a person skilled in the art, without inventive effort, further drawings may be derived from the following figures.
FIG. 1 is the chemical structure of beta-N-methylamino-L-alanine;
FIG. 2 is a chemical structural formula of N-acryloylalanine;
FIG. 3 is a chemical structure of anthracene-bridged quaternized vinylimidazole;
FIG. 4 is a chemical structure of a quaternized vinylimidazolium salt.
Detailed Description
The invention is further described with reference to the following examples.
Example 1
A beta-N-methylamino-L-alanine molecularly imprinted polymer is prepared by mixing template molecules, functional monomers, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, and performing cross-linking polymerization; wherein the content of the first and second substances,
the template molecule is beta-N-methylamino-L-alanine;
the functional monomers comprise N-acryloyl alanine, anthracene bridged quaternized vinyl imidazole and quaternized vinyl imidazolium salt;
the molar ratio of the template molecule to the functional monomer is 1:12, the molar ratio of the functional monomer to the cross-linking agent, the pore-foaming agent and the initiator is 1:1.5:35:0.06;
the mol ratio of N-acryloyl alanine, anthracene bridging quaternized vinyl imidazole and quaternized vinyl imidazolium salt in the functional monomer is 3:1.5:1.2;
the cross-linking agent is N, N' -methylene bisacrylamide or pentaerythritol tetraacrylate; the pore-foaming agent is acetone and dichloromethane; the initiator is an initiation system compounded by azodiisobutyronitrile and azodiisoheptonitrile;
the preparation method comprises the following steps:
s1, weighing beta-N-methylamino-L-alanine, a functional monomer, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, firstly placing the beta-N-methylamino-L-alanine and the functional monomer into a reactor, adding the pore-forming agent, stirring until the beta-N-methylamino-L-alanine and the functional monomer are completely dissolved, standing for 4-10h, adding the cross-linking agent and the initiator, fully mixing and stirring uniformly, introducing nitrogen to remove oxygen, sealing a reaction system, replacing reaction atmosphere with nitrogen, controlling the reaction temperature to be 60-80 ℃ in a constant-temperature water bath, and carrying out heat preservation polymerization reaction for 24h to obtain a polymerization product;
s2, crushing and grinding the polymerization product, sieving the polymerization product by a 200-mesh sieve, sufficiently eluting the sieved polymerization product by eluent until no beta-N-methylamino-L-alanine is washed out, and then washing and vacuum drying the product to prepare the beta-N-methylamino-L-alanine molecularly imprinted polymer;
wherein the eluent is a mixed solution of methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is 9:1.
the preparation method of the anthracene bridged quaternized vinyl imidazole comprises the following steps:
(1) Accurately weighing 10g of anthracene, 5g of trioxymethylene, 0.2g of hexadecyl trimethyl ammonium bromide and 15g of glacial acetic acid according to parts by weight, fully stirring and mixing, dropwise adding 52g of 47wt.% hydrobromic acid solution while stirring, continuously stirring for 1-20min after dropwise adding is finished, heating to 70-80 ℃, preserving heat, stirring for reaction for 4-5h, cooling after the reaction is finished, filtering, washing precipitates with deionized water, drying, and recrystallizing with toluene to obtain a bromomethylation product;
(2) Weighing 2g of bromomethylation product and 1.4g of vinyl imidazole, adding 52g of toluene, 52g of 10mol/L potassium hydroxide solution and 0.4g of n-butyl alcohol, fully stirring and mixing, heating and refluxing for 10-12h, cooling after the reaction is finished, filtering, washing the filtrate with deionized water, drying an oil layer with anhydrous magnesium sulfate or anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and recrystallizing the chloroform-cyclohexane mixed solution mixed in an equal volume ratio to obtain anthracene-bridged imidazole;
(3) Weighing 2g of anthracene-bridged imidazole, adding 20g of isopropanol, fully mixing and stirring uniformly, heating to 60-70 ℃, dropwise adding 0.9g of bromopropylene, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction for 12-14h, cooling after the reaction is finished, distilling off the bromopropylene at normal pressure, distilling off the isopropanol at reduced pressure, recrystallizing the product from an acetone-ethyl acetate mixed solution mixed in equal volume ratio, and drying to obtain the anthracene-bridged imidazole;
the preparation method of the quaternized vinyl imidazolium salt comprises the following steps:
according to a molar ratio of 1.2:1, weighing vinyl imidazole and bromoalkane, dissolving the vinyl imidazole and the bromoalkane in isopropanol, fully mixing and stirring uniformly, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction at 70-80 ℃ for 20 hours, and carrying out reduced pressure distillation to remove the isopropanol after the reaction is finished to obtain the quaternized vinyl imidazolium salt.
Example 2
A beta-N-methylamino-L-alanine molecularly imprinted polymer is prepared by mixing template molecules, functional monomers, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, and performing cross-linking polymerization; wherein, the first and the second end of the pipe are connected with each other,
the template molecule is beta-N-methylamino-L-alanine;
the functional monomers comprise N-acryloyl alanine, anthracene bridged quaternized vinyl imidazole and quaternized vinyl imidazolium salt;
the molar ratio of the template molecule to the functional monomer is 1:12, the molar ratio of the functional monomer to the cross-linking agent, the pore-foaming agent and the initiator is 1:1.5:35:0.06;
the mol ratio of N-acryloyl alanine, anthracene bridging quaternized vinyl imidazole and quaternized vinyl imidazolium salt in the functional monomer is 3:1:1;
the cross-linking agent is N, N' -methylene bisacrylamide or pentaerythritol tetraacrylate; the pore-foaming agent is acetone and dichloromethane; the initiator is an initiation system compounded by azodiisobutyronitrile and azodiisoheptonitrile;
the preparation method comprises the following steps:
s1, weighing beta-N-methylamino-L-alanine, a functional monomer, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, firstly placing the beta-N-methylamino-L-alanine and the functional monomer into a reactor, adding the pore-forming agent, stirring until the beta-N-methylamino-L-alanine and the functional monomer are completely dissolved, standing for 4-10h, adding the cross-linking agent and the initiator, fully mixing and stirring uniformly, introducing nitrogen to remove oxygen, sealing a reaction system, replacing reaction atmosphere with nitrogen, controlling the reaction temperature to be 60-80 ℃ in a constant-temperature water bath, and carrying out heat preservation polymerization reaction for 24h to obtain a polymerization product;
s2, crushing and grinding the polymerization product, sieving the obtained product by using a 200-mesh sieve, sufficiently eluting the sieved polymerization product by using an eluent until no beta-N-methylamino-L-alanine is washed out, washing and then drying in vacuum to obtain the beta-N-methylamino-L-alanine molecularly imprinted polymer;
wherein the eluent is a mixed solution of methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is 9:1.
the preparation method of the anthracene-bridged quaternized vinyl imidazole comprises the following steps:
(1) Accurately weighing 10g of anthracene, 5g of trioxymethylene, 0.2g of hexadecyl trimethyl ammonium bromide and 15g of glacial acetic acid according to parts by weight, fully stirring and mixing, dropwise adding 52g of 47wt.% hydrobromic acid solution while stirring, continuously stirring for 1-20min after dropwise adding is finished, heating to 70-80 ℃, keeping the temperature and stirring for reaction for 4-5h, cooling after the reaction is finished, filtering, washing precipitates with deionized water, drying, and recrystallizing with toluene to obtain a bromomethylation product;
(2) Weighing 2g of bromomethylation product and 1.4g of vinyl imidazole, adding 52g of toluene, 52g of 10mol/L potassium hydroxide solution and 0.4g of n-butyl alcohol, fully stirring and mixing, heating and refluxing for 10-12h, cooling after the reaction is finished, filtering, washing the filtrate with deionized water, drying an oil layer with anhydrous magnesium sulfate or anhydrous sodium sulfate, evaporating the solvent under reduced pressure, and recrystallizing the chloroform-cyclohexane mixed solution mixed in an equal volume ratio to obtain anthracene-bridged imidazole;
(3) Weighing 2g of anthracene bridged imidazole, adding 20g of isopropanol, fully mixing and stirring uniformly, heating to 60-70 ℃, dropwise adding 0.9g of bromopropylene, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction for 12-14h, cooling after the reaction is finished, steaming at normal pressure to remove the bromopropylene, steaming at reduced pressure to remove the isopropanol, recrystallizing the product from an acetone-ethyl acetate mixed solution mixed in equal volume ratio, and drying to obtain the anthracene bridged imidazole;
the preparation method of the quaternized vinyl imidazolium salt comprises the following steps:
according to a molar ratio of 1.2:1, weighing vinyl imidazole and bromoalkane, dissolving the vinyl imidazole and the bromoalkane in isopropanol, fully mixing and stirring uniformly, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction at 70-80 ℃ for 20 hours, and carrying out reduced pressure distillation to remove the isopropanol after the reaction is finished to obtain the quaternized vinyl imidazolium salt.
Example 3
The beta-N-methylamino-L-alanine surface molecularly imprinted polymer comprises an inert mesoporous microsphere carrier and a molecularly imprinted polymer covering the surface of a porous carrier, wherein the inert mesoporous microsphere carrier is silicon dioxide;
the preparation method comprises the following steps:
s1, adding 2g of mesoporous silica carrier into 1mol/L dilute hydrochloric acid solution for soaking and cleaning, and then washing with distilled water to be neutral to obtain activated silica; adding 40ml of toluene into the activated silicon dioxide, adding 2ml of 4- (chloromethyl) phenyl trimethoxy silane, reacting for 3 hours at 150 ℃ under the protection of nitrogen, filtering, collecting precipitate, cleaning with acetone, and drying in vacuum to obtain a modified mesoporous silicon dioxide carrier;
s2, weighing beta-N-methylamino-L-alanine, a functional monomer, a cross-linking agent, a pore-forming agent and an initiator according to the molar ratio in the embodiment 1, firstly placing the beta-N-methylamino-L-alanine and the functional monomer in a reactor, adding the pore-forming agent, stirring until the beta-N-methylamino-L-alanine and the functional monomer are completely dissolved, standing for 4-10h, adding the cross-linking agent and the modified mesoporous carrier, adding the initiator after uniformly mixing, fully mixing and stirring uniformly, introducing nitrogen, deoxidizing, closing a reaction system, replacing the reaction atmosphere with nitrogen, and carrying out polymerization reaction under a thermal initiation condition to obtain a surface imprinting product;
the cross-linking agent is N, N' -methylene bisacrylamide or pentaerythritol tetraacrylate; the pore-foaming agent is acetone and dichloromethane; the initiator is an initiation system compounded by azodiisobutyronitrile and azodiisoheptonitrile;
s3, washing the surface imprinting product with acetone and dichloromethane, sufficiently eluting the surface imprinting product with an eluent until no beta-N-methylamino-L-alanine is eluted, washing with ethanol, and drying in vacuum to obtain the beta-N-methylamino-L-alanine surface molecularly imprinted polymer.
Comparative example
The preparation method is the same as example 1 except that no template molecule is added.
Examples of the experiments
Putting 4mg of molecularly imprinted polymer into 2ml centrifuge tubes, adding 1.5ml of BMAA standard solution or beta-amino-N-methylalanine (BAMA) solution with different concentrations into each centrifuge tube, oscillating for 4h at room temperature, centrifuging, measuring the BMAA concentration in the supernatant respectively, simultaneously adsorbing by parallel non-imprinted polymers, measuring the maximum adsorption capacity respectively, calculating the maximum imprinting factor (the ratio of the maximum adsorption amount of the molecularly imprinted polymer to the BMAA to the maximum adsorption amount of the non-imprinted polymer to the BMAA) and measuring the selection factor for the beta-amino-N-methylalanine (the ratio of the maximum adsorption amount of the molecularly imprinted polymer to the BMAA to the maximum adsorption amount of the molecularly imprinted polymer to the BAMA), and the result is shown in Table 1.
TABLE 1 adsorption Performance results for molecularly imprinted polymers
Figure BDA0002997847160000081
Finally, it should be noted that the above embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the protection scope of the present invention, although the present invention is described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. The beta-N-methylamino-L-alanine molecularly imprinted polymer is characterized by being prepared by mixing template molecules, functional monomers, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, and performing cross-linking polymerization; wherein the content of the first and second substances,
the template molecule is beta-N-methylamino-L-alanine;
the functional monomers comprise N-acryloyl alanine, anthracene bridged quaternized vinyl imidazole and quaternized vinyl imidazolium salt;
the molar ratio of the template molecule to the functional monomer is 1: (7-20), wherein the molar ratio of the functional monomer to the cross-linking agent, the pore-forming agent and the initiator is 1: (0.5-5): (20-45): (0.05-0.1);
the molar ratio of N-acryloyl alanine, anthracene bridging quaternized vinyl imidazole and quaternized vinyl imidazolium salt in the functional monomer is (1-4): (0.1-3): (1-3);
the preparation method of the anthracene bridged quaternized vinyl imidazole comprises the following steps:
a1, accurately weighing 1 part of anthracene, 0.5 part of trioxymethylene, 0.02 part of hexadecyl trimethyl ammonium bromide and 1.5 parts of glacial acetic acid according to parts by weight, fully stirring and mixing, dropwise adding 5.2 parts of 47wt.% hydrobromic acid solution while stirring, continuously stirring for 1-20min after dropwise adding is finished, heating to 70-80 ℃, carrying out heat preservation and stirring for reaction for 4-5h, cooling after the reaction is finished, filtering, washing precipitates with deionized water, drying, and recrystallizing with toluene to obtain a bromomethylation product;
a2, weighing 2 parts of bromomethylation product and 1.4 parts of vinyl imidazole, adding 52 parts of toluene, 52 parts of 10mol/L potassium hydroxide solution and 0.4 part of n-butyl alcohol, fully stirring and mixing, heating and refluxing for 10-12h, cooling after the reaction is finished, filtering, washing the filtrate with deionized water, drying an oil layer with anhydrous magnesium sulfate or anhydrous sodium sulfate, then evaporating the solvent under reduced pressure, and recrystallizing the chloroform-cyclohexane mixed solution with the same volume ratio to obtain anthracene-bridged imidazole;
and A3, weighing 2 parts of anthracene bridged imidazole, adding 20 parts of isopropanol, fully mixing and stirring uniformly, heating to 60-70 ℃, dropwise adding 0.9 part of bromopropylene, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction for 12-14h, cooling after the reaction is finished, steaming to remove the bromopropylene at normal pressure, steaming to remove the isopropanol at reduced pressure, recrystallizing the product from acetone-ethyl acetate mixed solution mixed in equal volume ratio, and drying to obtain the anthracene bridged imidazole.
2. The beta-N-methylamino-L-alanine molecularly imprinted polymer according to claim 1, wherein the cross-linking agent is N, N '-methylenebisacrylamide, N' -1,4-phenylenebisacrylamide, pentaerythritol triacrylate, pentaerythritol tetraacrylate, trimethylolpropane trimethacrylate, 3,5-di (acrylamide) benzoic acid or ethylene glycol dimethacrylate; the pore-foaming agent is one or two of dimethyl sulfoxide, isopropanol, acetone, dichloromethane, chloroform and carbon tetrachloride; the initiator is organic peroxide or azo compound.
3. The beta-N-methylamino-L-alanine molecularly imprinted polymer according to claim 2, wherein the cross-linking agent is N, N' -methylenebisacrylamide or pentaerythritol tetraacrylate.
4. The method for preparing the beta-N-methylamino-L-alanine molecularly imprinted polymer according to one of claims 1 to 3, characterized by comprising the following steps:
s1, weighing the beta-N-methylamino-L-alanine, the functional monomer, the cross-linking agent, the pore-forming agent and the initiator according to a molar ratio, firstly placing the beta-N-methylamino-L-alanine and the functional monomer into a reactor, adding the pore-forming agent, stirring until the beta-N-methylamino-L-alanine and the functional monomer are completely dissolved, standing for 4-10h, adding the cross-linking agent and the initiator, fully mixing and stirring uniformly, introducing nitrogen to remove oxygen, closing a reaction system, replacing reaction atmosphere with nitrogen, and carrying out polymerization reaction under a thermal initiation or photo initiation condition to obtain a polymerization product;
s2, sequentially crushing, grinding and sieving the polymerization product with a 200-mesh sieve, sufficiently eluting the sieved polymerization product with eluent until no beta-N-methylamino-L-alanine is washed out, and washing and then drying in vacuum to obtain the beta-N-methylamino-L-alanine molecularly imprinted polymer;
wherein the eluent is a mixed solution of methanol and acetic acid, and the volume ratio of the methanol to the acetic acid is (6-10): 1.
5. the method for preparing the beta-N-methylamino-L-alanine molecularly imprinted polymer according to claim 4, wherein the thermal initiation conditions are as follows: controlling the reaction temperature in a constant-temperature water bath at 60-80 ℃, and carrying out heat preservation reaction for 12-36h; the photoinitiated conditions were: reacting for 12-36h under a high-pressure mercury lamp.
6. The method for preparing the beta-N-methylamino-L-alanine molecularly imprinted polymer according to claim 4, characterized in that the method for preparing the quaternized vinyl imidazolium salt comprises the following steps:
according to a molar ratio (1-1.2): 1, weighing vinyl imidazole and bromoalkane, dissolving the vinyl imidazole and the bromoalkane in isopropanol, fully mixing and stirring uniformly, closing a reaction system, replacing the reaction atmosphere with nitrogen, carrying out reflux reaction at 70-80 ℃ for 16-24h, and carrying out reduced pressure distillation to remove the isopropanol after the reaction is finished to obtain the quaternized vinyl imidazolium salt.
7. A beta-N-methylamino-L-alanine surface molecularly imprinted polymer, which is characterized by comprising an inert mesoporous microsphere carrier and a molecularly imprinted polymer covering the surface of the inert mesoporous microsphere carrier, wherein the molecularly imprinted polymer is the molecularly imprinted polymer according to any one of claims 1 to 3.
8. The beta-N-methylamino-L-alanine surface molecularly imprinted polymer according to claim 7, wherein the inert mesoporous microsphere carrier is silica gel, silica dioxide, polyvinyl chloride, polystyrene or activated carbon.
9. The method for preparing the beta-N-methylamino-L-alanine surface molecularly imprinted polymer according to claim 7, characterized by comprising the following steps:
b1, adding the inert mesoporous carrier into a dilute acid solution for soaking and cleaning, washing the inert mesoporous carrier to be neutral by distilled water to obtain an activated mesoporous carrier, and performing surface modification on the activated mesoporous carrier by using a silane coupling agent to obtain a modified mesoporous carrier; wherein the concentration of hydrogen ions in the dilute acid solution is 0.1-2mol/L; the silane coupling agent is 4- (chloromethyl) phenyl trimethoxy silane, vinyl trimethoxy silane or gamma-methacryloxy propyl trimethoxy silane;
b2, weighing beta-N-methylamino-L-alanine, a functional monomer, a cross-linking agent, a pore-forming agent and an initiator according to a molar ratio, firstly placing the beta-N-methylamino-L-alanine and the functional monomer into a reactor, adding the pore-forming agent, stirring until the beta-N-methylamino-L-alanine and the functional monomer are completely dissolved, standing for 4-10h, adding the cross-linking agent and the modified mesoporous carrier, uniformly mixing, adding the initiator, uniformly mixing and stirring, introducing nitrogen, removing oxygen, closing a reaction system, replacing reaction atmosphere with nitrogen, and carrying out polymerization reaction under a thermal initiation or photo initiation condition to obtain a surface imprinting product;
and B3, washing the surface imprinting product by using a pore-foaming agent, sufficiently eluting the surface imprinting product by using an eluent until no beta-N-methylamino-L-alanine is eluted, washing again, and then drying in vacuum to obtain the beta-N-methylamino-L-alanine surface molecularly imprinted polymer.
CN202110336327.6A 2021-03-29 2021-03-29 beta-N-methylamino-L-alanine molecularly imprinted polymer Active CN112920323B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110336327.6A CN112920323B (en) 2021-03-29 2021-03-29 beta-N-methylamino-L-alanine molecularly imprinted polymer

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110336327.6A CN112920323B (en) 2021-03-29 2021-03-29 beta-N-methylamino-L-alanine molecularly imprinted polymer

Publications (2)

Publication Number Publication Date
CN112920323A CN112920323A (en) 2021-06-08
CN112920323B true CN112920323B (en) 2022-10-11

Family

ID=76176487

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110336327.6A Active CN112920323B (en) 2021-03-29 2021-03-29 beta-N-methylamino-L-alanine molecularly imprinted polymer

Country Status (1)

Country Link
CN (1) CN112920323B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003509550A (en) * 1999-09-17 2003-03-11 エムアイピー・テクノロジーズ・エービー Novel molecularly imprinted polymer grafted on solid support
CN103833915B (en) * 2012-11-20 2018-04-13 南开大学 Molecularly imprinted polymer nano particle suitable for pure biological sample and preparation method thereof
US10159638B2 (en) * 2016-06-21 2018-12-25 Johnson & Johnson Consumer Inc. Personal care compositions containing complexing polyelectrolytes
ES2686136B1 (en) * 2017-03-29 2019-08-14 Univ Castilla La Mancha 9,10-BIS SYNTHESIS PROCEDURE (CHLOROME) ANTRACENE
CN108864364B (en) * 2018-06-11 2021-02-02 西京学院 Preparation method of L-phenylalanine molecularly imprinted polymer
CN108997218B (en) * 2018-08-27 2020-03-31 嘉兴学院 Fluorescent functional monomer, molecularly imprinted polymer, and preparation method and application thereof
WO2020046210A1 (en) * 2018-08-29 2020-03-05 National University Of Singapore A molecularly imprinted polymer and method of making the same

Also Published As

Publication number Publication date
CN112920323A (en) 2021-06-08

Similar Documents

Publication Publication Date Title
US4439545A (en) Acrylic copolymers of N-acryloylpolymethyleneimines or N-acryloyldialkylamides, N,N'-acryloyldiaminoalcanes and N-acryloylaminoacids (or esters) their preparation and use as cation exchangers
CN109400771B (en) Preparation method and application of super-crosslinked porous polyion liquid material
WO2012081727A1 (en) Temperature-responsive adsorbent having strong cation exchange group, and method for producing same
JPS5858026B2 (en) Packing material for chromatography and its manufacturing method
CN109400922B (en) Preparation method and application of super-crosslinked porous polyion liquid material
CN113018506B (en) Composite polyacrylamide hydrogel and preparation method thereof
CN112675824A (en) Fe3O4Chemically grafted polyacrylic acid-chitosan composite hydrogel and preparation method thereof
CN106146716B (en) A kind of OPC B2Molecularly imprinted polymer and its preparation method and application
CN106111093A (en) A kind of remove the preparation method of the hybridized film of copper ion in water
CN112920323B (en) beta-N-methylamino-L-alanine molecularly imprinted polymer
CN111171212A (en) Metal organic framework surface molecularly imprinted polymer and preparation method and application thereof
CA2518557C (en) Methods for producing macromolecule identifying polymers
CN106866900A (en) A kind of photoresponse molecularly imprinted material on surface and its preparation method and application
CN104877090B (en) A kind of room temperature ultraviolet method and the application that trigger polymerization to prepare ion imprinted polymer
CN113145083B (en) Janus bifunctional blotting membrane and preparation method and application thereof
CN103111260B (en) Preparation method of dumbbell-shaped molecular imprinting stirring rod
CN108752524B (en) Preparation method of lysozyme molecular imprinting temperature-sensitive hydrogel
CN109021173B (en) Preparation method of thymopentin molecularly imprinted core-shell microspheres
RU2439089C1 (en) Method of producing cellular polymer sorbent for selective sorption of endotoxin from blood plasma
CN114560964A (en) Synthetic method and application of carboxyl functional polyion liquid
CN109721759B (en) Acetyl glucosamine imprinted material and application thereof in recognition of acetyl glucosamine and acetyl glucosamine modified peptide fragment
CN110776596A (en) Para-hydroxybenzoic acid selective resin and preparation method thereof
CN109400923A (en) A kind of preparation method and application of super cross-linked porous poly ion liquid material
CN112871147B (en) Preparation method of chromatography medium for removing multimers in monoclonal antibodies
JPH0788366A (en) Production of separating agent

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant