CN109438620B - Molecularly imprinted polymer with reversible covalent binding function and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a molecularly imprinted polymer with a reversible covalent binding function, and a preparation method and application thereof. Introducing a covalent bond in a Molecularly Imprinted Polymer (MIPs) system by taking Dopamine (DA) as a template and 4-vinyl phenylboronic acid (VPBV) as a functional monomer, and self-assembling the covalent bond with a cross-linking agent and an initiator to form a covalent imprinted polymer; adjusting the pH value of the environment to be acidic to break the covalent bond, and separating the DA template from the MIPs so as to form a cavity complementary with the 3D shape of the DA; when the pH is more than 5, the boric acid of VPBV can be covalently combined with the vicinal diol of DA again, and the recognition function of DA is realized. The invention combines the advantages of molecular imprinting space structure and borate affinity to realize the improvement of the selectivity and sensitivity of DA detection. The invention provides the DA detection with obviously improved sensitivity, can be recycled, saves the cost, is nontoxic and harmless, and shows that the method is a promising DA analysis method.
Description
Technical Field
The invention relates to the technical field of material chemistry, in particular to a molecularly imprinted polymer with a reversible covalent binding function, and a preparation method and application thereof.
Background
As highly desirable artificial chemical receptors, Molecularly Imprinted Polymers (MIPs) have become a general material for predictability, specificity identifiability, and based on their molecularly imprinted specific structures. It should be noted, however, that the functional monomer molecules and template molecules of conventional MIPs are produced by non-covalent interactions, such as hydrogen bonding, van der waals forces, and static attraction. It should be noted that the structural consistency of the non-covalently bound monomer-template conjugates in the prepolymer cannot be guaranteed and the generation of non-specific binding sites due to the random grafting of the functional monomers and cross-linkers into the polymer matrix is often unstable, resulting in low binding capacity, slow kinetics and inaccurate recognition.
It is well known that boronic acids covalently interact with cis-alcohols at relatively high pH values to form stable cyclic esters, whereas boronic esters dissociate upon transition to acidic at ambient pH, due to their reversible binding capacity. Boric acid groups are considered to be ideal electrochemical sensors. Unfortunately, borate affinity materials suffer from several disadvantages, such as exhibiting a class of selectivity for cis-diol-containing compounds. It is difficult to provide accurate bonding characteristics.
Dopamine (DA) is one of the important neurotransmitters and plays a key role in the function of the central nervous system and the hormonal system. Lack or alteration of neuronal release and DA uptake will induce brain diseases such as schizophrenia and HIV infection. Therefore, there is still a need for reliable DA detection. Mass spectrometry for DA analysis has been proposed so far, such as surface blotting, epitope blotting and adhesive emulsions. However, the utility and simple method of DA quantification has not been reported.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a molecularly imprinted polymer with reversible covalent binding function and a preparation method and application thereof.
The invention is realized by the following technical scheme:
a preparation method of a molecularly imprinted polymer with a reversible covalent binding function comprises the steps of introducing a covalent bond into a Molecularly Imprinted Polymer (MIPs) system by taking Dopamine (DA) as a template and 4-vinyl phenylboronic acid (VPBV) as a functional monomer, and self-assembling the covalently imprinted polymer with a cross-linking agent and an initiator; the environmental pH is then adjusted to acidity to break the covalent bonds and the DA template is detached from the MIPs, thereby forming a cavity complementary to the 3D shape of the DA. When the pH is more than 5, the boric acid of VPBV can be covalently combined with the vicinal diol of DA again, and the recognition function of DA is realized.
The preparation method according to claim 1, which is characterized by comprising the following steps:
synthesis of covalent-MIPs: dissolving template Dopamine (DA), functional monomer 4-vinyl phenylboronic acid (VPBV), cross-linking agent Ethylene Glycol Dimethacrylate (EGDMA) and free radical initiator (AIBN) in acetonitrile and DMF; sonicate the mixture for 10 minutes to maintain homogeneity; then using N2The solution was purged with gas for 15 minutes and at N2Sealing under atmosphere; finally, immersing the flask in an oil bath at the temperature of 50-80 ℃ for polymerization for 24 hours;
removing the membrane plate: the template was removed by alternate solvent extraction with methanol/acetic acid and hydrochloric acid solution (pH 2); complete removal of the template was confirmed by ultraviolet absorption spectroscopy (UV); the resulting polymer was then dried under vacuum at 40 ℃ overnight.
The preparation method comprises the following steps of: adding 1-20 mmol of functional monomer VPBV, 1-40 mmol of cross-linking agent EGDMA and 10-60 mg of free radical initiator into 1mmol of template DA, and dissolving in 10-300 mL of acetonitrile and 10-200 mL of DMDMF.
According to the preparation method, the volume ratio of methanol to acetic acid is 8/2, and the pH value of a hydrochloric acid solution is 2.
The preparation method comprises the steps of firstly mixing template Dopamine (DA), functional monomer VPBV, solvent acetonitrile and DMF to form a prepolymer, reacting for 10-20 min, then adding cross-linking agent EGDMA and initiator AIBN, and polymerizing in an oil bath at 50-80 ℃.
The preparation method comprises the following steps of: dissolving 1mmol of template DA, 2mmol of functional monomer VPBV, 2mmol of EGDMA and a free radical initiator AIBN25mg in 25mL of acetonitrile and 15mL of DMF; mixing the raw materialsSonicating the material for 10 minutes to maintain homogeneity; then with mild N2The solution was purged with a gas flow for 15 minutes at N2Sealing under atmosphere; finally the flask was immersed in an oil bath at 70 ℃ for polymerization for 24 hours.
According to the preparation method, external stirring is not needed in the whole reaction process, so that the influence on the appearance of the MIPs is avoided.
The molecularly imprinted polymer with reversible covalent binding function prepared by any one of the preparation methods.
The molecularly imprinted polymer with the reversible covalent binding function is applied to detecting trace DA.
The application method comprises the following steps:
preparation of the film: after removing the template, 360mg of covalent-MIPs (6 wt%), cation exchanger NaTFPB (1 wt%), high-molecular polyvinyl chloride PVC (35.6 wt%) and plasticizer NPOE (53.4 wt%) are dissolved in 3.5mL of tetrahydrofuran solution, sealed by a sealing film, and stirred vigorously for 5 hours to be mixed uniformly; then transferring the membrane components into a ring of 3.6cm by using a 5mL liquid transfer gun, and putting the ring into a constant temperature and humidity cabinet for drying for at least 12h to completely volatilize tetrahydrofuran serving as a solvent in the membrane so as to form a transparent and uniform polymer membrane;
self-assembled working electrode: the film was cut into circular slices of 5mm in diameter with a punch and adhered to the top of a PVC pipe with tetrahydrofuran; the electrode internal filling solution is 0.01mol/L NaCl solution, the electrode activating solution is 30mmol/LpH ═ 7.5 phosphoric acid buffer solution, and the electrode needs to be activated in the activating solution for 12 hours before electrode detection;
potential detection: a self-assembled working electrode and a double-liquid-connection saturated calomel electrode with 0.1mol/LLIOAc as a salt bridge electrolyte are used as reference electrodes, and a PXSJ-216 type thunder magnetic ion meter is used for carrying out potential detection on the trace DA.
Compared with non-imprinted polymer (NIPs) materials, the present invention has the following advantages:
1. the invention introduces boric acid group for molecular recognition for the first time, the covalent bond bonding force is strong, and the template-monomer structure is stable.
2. The invention can destroy boric acid cyclic ester by adjusting the pH of the environment to be 2, dissociate template molecules, and realize the repeated use of MIPs, wherein the removal rate of the template molecules is more than 98%.
3. The invention combines the advantages of molecular imprinting space structure and borate affinity to realize the improvement of selectivity and sensitivity of DA detection.
4. The whole process of the invention is nontoxic and pollution-free, has low cost, simple operation and good effect.
Drawings
FIG. 1 is a schematic diagram of the method for recognizing trace dopamine by using a molecularly imprinted polymer with reversible covalent binding function according to the method of the invention.
FIG. 2 is a reversible assay of the bonding force of MIPs and NIPs imprinting molecules.
FIG. 3 is an electrode potential response graph of MIPs and NIPs used in the detection of DA in the ionic state by the polymer membrane ion-selective electrode;
Detailed Description
The present invention will be described in detail with reference to specific examples.
Example 1
The invention discloses a preparation method of a molecularly imprinted polymer with reversible covalent binding function, which comprises the following steps:
synthesis of covalent-MIPs: 1mmol of template DA, 2mmol of functional monomer 4-vinylphenylboronic acid (VPBV), 2mmol of crosslinking agent Ethylene Glycol Dimethacrylate (EGDMA) and free radical initiator AIBN25mg were dissolved in acetonitrile (25mL) and DMF (15 mL). The mixture was sonicated for 10 minutes to maintain homogeneity. Then with mild N2The solution was purged with a gas flow for 15 minutes at N2And sealing under the atmosphere. Finally the flask was immersed in an oil bath at 70 ℃ for polymerization for 24 hours.
Removing the membrane plate: the template was removed by alternate solvent extraction with methanol/acetic acid (8/2, v/v) and hydrochloric acid solution (pH 2). Complete removal of the template was confirmed by ultraviolet absorption spectroscopy (UV). The resulting polymer was then dried under vacuum at 40 ℃ overnight.
Among them, 4-vinylphenylboronic acid (VPBV), Ethylene Glycol Dimethacrylate (EGDMA), Dopamine (DA) and 2,2' -azobis (isobutyronitrile) (AIBN) are commercially available, and methanol, acetic acid and acetonitrile are analytically pure products.
Wherein, no external stirring is needed in the whole reaction process, and the stirring will influence the appearance of the MIPs.
Preparation of the film: after removing the template, 360mg of covalent-MIPs (6 wt%), cation exchanger NaTFPB (1 wt%), high-molecular polyvinyl chloride PVC (35.6 wt%), and plasticizer NPOE (53.4 wt%) were dissolved in 3.5mL of tetrahydrofuran solution, sealed with a sealing film, and vigorously stirred for 5h to mix them uniformly. Then transferring the membrane components into a ring of 3.6cm by using a 5mL liquid transfer gun, and placing the ring in a constant temperature and humidity cabinet for drying for at least 12h to completely volatilize tetrahydrofuran which is a solvent in the membrane so as to form a transparent and uniform polymer membrane with the thickness of about 200 mu m.
Self-assembled working electrode: the film was cut into a circular section having a diameter of 5mm using a punch and adhered to the tip of a PVC tube (the PVC tube was ultrasonically washed three times each with ethanol and ultrapure water alternately before use and then dried in an oven) with tetrahydrofuran. The electrode internal solution is 0.01mol/L NaCl solution, the electrode activating solution is 30mmol/LpH ═ 7.5 phosphoric acid buffer solution, and the electrode needs to be activated in the activating solution for 12h before electrode detection.
Potential detection: trace DA (concentration: 10) by using PXSJ-216 type thunder magnetic ion meter-6-10-2mol/L) and using a double-liquid connection saturated calomel electrode which is a self-assembled working electrode and 0.1mol/LLIOAc as a salt bridge electrolyte as a reference electrode.
FIG. 2 shows reversible measurements of the bonding force between MIPs and NIPs. The MIPs and NIPs are continuously immersed in a liquid containing 10-4mol/L DA solution in acid (pH 2.0, odd cycles) and alkaline (pH 5.5, even cycles). It can be seen from the figure that the molecularly imprinted polymer has much stronger adsorption to DA than non-molecularly imprinted polymers because the molecularly imprinted polymer has a specific recognition site for DA, and binding to DA is formed by specific recognition (covalent bond). Whereas, NIPs do not have specific recognition sites, binding to DA is formed by non-specific recognition (surface adsorption).
FIG. 3 shows MIPs and NIPs for polymersThe membrane ion selective electrode detects an electrode potential response pattern of DA in an ionic state. The conventional potential response curves are shown in the graph, with MIPs-based sensors (upper curve) having better response and higher sensitivity than NIPs-based sensors (lower curve). MIPs particle based sensors are at 10-6-10-2The mol/L concentration range exhibited a better Nernst response, whereas the NIPs particle-based sensors deviated significantly from the Nernst response in this range and were at 10-6-10-5The mol/L concentration range is almost unresponsive. The improvement in sensitivity derives mainly from the MIPs particles combining the advantages of molecular imprinting steric structure and borate affinity.
Example 2
Synthesis of covalent-MIPs: template DA (1mmol), functional monomer VPBV (2mmol), EGDMA (10mmol) and free radical initiator AIBN (20mg) were dissolved in acetonitrile (45mL) and DMF (15 mL). The mixture was sonicated for 10 minutes to maintain homogeneity. Then using N2The solution was purged with gas for 15 minutes and at N2And sealing under the atmosphere. Finally the flask was immersed in an oil bath at 70 ℃ for polymerization for 24 hours.
Removing the membrane plate: the template was removed by batch mode solvent extraction with methanol/acetic acid (8/2, v/v) and hydrochloric acid solution (pH 2). Complete removal of the template was confirmed by ultraviolet absorption spectroscopy (UV). The resulting polymer was then dried under vacuum at 40 ℃ overnight.
The synthesis method of the covalent-MIPs comprises the following steps:
template DA (1mmol), functional monomer VPBV (2mmol), EGDMA (10mmol) and free radical initiator AIBN (20mg) were dissolved in acetonitrile (45mL) and DMF (15 mL). The mixture was sonicated for 10 minutes to maintain homogeneity. Then using N2The solution was purged with gas for 15 minutes and at N2And sealing under the atmosphere. Finally, the flask is immersed in an oil bath at 50-80 ℃ for polymerization for 24 hours.
Example 3
Synthesis of covalent-MIPs: template DA (1mmol), functional monomer VPBV (2mmol), EGDMA (10mmol) and free radical initiator AIBN (20mg) were dissolved in acetonitrile (45mL) and DMF (15 mL). The mixture was sonicated for 10 minutes to maintain homogeneity. Then using N2The solution was purged with gas for 15 minutes and at N2And sealing under the atmosphere. Finally the flask was immersed in an oil bath at 80 ℃ for polymerization for 24 hours.
Removing the membrane plate: the template was removed by batch mode solvent extraction with methanol/acetic acid (8/2, v/v) and hydrochloric acid solution (pH 2). Complete removal of the template was confirmed by ultraviolet absorption spectroscopy (UV). The resulting polymer was then dried under vacuum at 40 ℃ overnight.
It will be understood that modifications and variations can be made by persons skilled in the art in light of the above teachings and all such modifications and variations are intended to be included within the scope of the invention as defined in the appended claims.
Claims (7)
1. A preparation method of a molecularly imprinted polymer with a reversible covalent binding function is characterized in that Dopamine (DA) is used as a template, 4-vinylphenylboronic acid is used as a functional monomer, a covalent bond is introduced into a Molecularly Imprinted Polymer (MIPs) system, and the covalent imprinted polymer is self-assembled with a cross-linking agent and an initiator; then adjusting the pH value of the environment to be acidic to break the covalent bond, and separating the DA template from the MIPs so as to form a cavity complementary with the 3D shape of the DA; the preparation process comprises the following steps:
synthesis of covalent-MIPs: dissolving template Dopamine (DA), functional monomer 4-vinyl phenylboronic acid, cross-linking agent Ethylene Glycol Dimethacrylate (EGDMA) and free radical initiator (AIBN) in acetonitrile and DMF; sonicate the mixture for 10 minutes to maintain homogeneity; then using N2The solution was purged with gas for 15 minutes and at N2Sealing under atmosphere; finally, immersing the flask in an oil bath at the temperature of 50-80 ℃ for polymerization for 24 hours; adding 1-20 mmol of functional monomer 4-vinyl phenylboronic acid, 1-40 mmol of cross-linking agent EGDMA and 10-60 mg of free radical initiator AIBN into every 1mmol of template DA, and dissolving in 10-300 mL of acetonitrile and 10-200 mL of DMDMMF;
removing the template: the template was removed by batch mode solvent extraction with methanol/acetic acid and hydrochloric acid solution; complete removal of the template was confirmed by ultraviolet absorption spectroscopy (UV); the resulting polymer was then dried under vacuum at 40 ℃ overnight.
2. The method according to claim 1, wherein the volume ratio of methanol/acetic acid is 8/2.
3. The preparation method of claim 1, wherein the covalent-MIPs are synthesized by mixing a template Dopamine (DA), a functional monomer 4-vinylphenylboronic acid, a solvent acetonitrile and DMF to form a prepolymer, reacting for 10-20 min, adding a cross-linking agent EGDMA and an initiator AIBN, and polymerizing in an oil bath at 50-80 ℃.
4. The method of claim 1, wherein the covalent-MIPs are synthesized by: dissolving 1mmol of template DA, 2mmol of functional monomer 4-vinyl phenylboronic acid, 2mmol of EGDMA and a free radical initiator AIBN25mg in 25mL of acetonitrile and 15mL of DMF; sonicate the mixture for 10 minutes to maintain homogeneity; then with mild N2The solution was purged with a gas flow for 15 minutes at N2Sealing under atmosphere; finally the flask was immersed in an oil bath at 70 ℃ for polymerization for 24 hours.
5. The preparation method according to any one of claims 1 to 4, wherein no external stirring is required during the whole reaction process, thereby avoiding affecting the morphology of MIPs.
6. A molecularly imprinted polymer having a reversible covalent bonding function prepared by the preparation method according to any one of claims 1 to 4.
7. Use of the molecularly imprinted polymer with reversible covalent binding function according to claim 6 for detecting trace DA.
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| CN103406109A (en) * | 2013-08-06 | 2013-11-27 | 南京大学 | Controllable and universal directional surface printing method and application of molecular printing polymer obtained via same |
| CN104020195A (en) * | 2014-05-27 | 2014-09-03 | 安徽师范大学 | Double recognition dopamine imprinting electrochemical sensor and preparation method and application thereof |
| WO2018160132A1 (en) * | 2017-02-28 | 2018-09-07 | National University Of Singapore | A method of making a molecularly imprinted polymer sensor |
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