CN111040003B - Chitosan oligosaccharide derivative molecular imprinting functional monomer and preparation method thereof - Google Patents
Chitosan oligosaccharide derivative molecular imprinting functional monomer and preparation method thereof Download PDFInfo
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Abstract
A chitosan oligosaccharide derivative molecular imprinting functional monomer and a preparation method thereof relate to the technical field of chemical industry, in particular to a design and production process of the molecular imprinting functional monomer. Dissolving asparagine, glutamine, methionine or threonine neutral amino acid and potassium carbonate in water, dropwise adding pentenoyl chloride under the condition of ice-water bath, and then placing at room temperature for reaction to prepare an N-pentenoyl-amino acid solution; and adjusting the pH value of the N-pentenoyl-amino acid solution to be neutral, mixing the solution with the chitosan oligosaccharide, EDC and NHS for reaction, dialyzing by using a dialysis bag, and freeze-drying to obtain the N- (N' -pentenoyl-amino acid acyl) -chitosan oligosaccharide. The method has the advantages of simple synthesis reaction, mild reaction conditions, high yield, preparation cost saving and capability of enabling the imprinted polymer to obtain more effective recognition sites.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a design and production process of a molecular imprinting functional monomer.
Background
Molecular imprinting is a technique for preparing a polymer having selective recognition ability for a specific molecule (also called a template molecule). The principle is as follows: in a proper medium, template molecules and functional monomers with proper functional groups form a certain host-guest complex, a cross-linking agent and an initiator are added to initiate polymerization, and then the template molecules are imprinted into a polymer. When the template molecule is removed, cavities with multiple sites of action are formed in the polymer that match the spatial configuration of the template molecule, such cavities having selective recognition properties for the template molecule and its analogs. Such polymers can also be referred to as artificial antibodies. In recent years, molecular imprinting technology has been widely applied to a plurality of fields such as chromatographic separation, solid phase extraction, drug analysis, biosensor technology, catalytic synthesis and the like, and thus, the molecular imprinting technology becomes one of the novel fields crossing chemistry and biology, shows good application prospects, and is rapidly developed.
It is very important to select proper functional monomers in the molecularly imprinted polymer, on one hand, the functional monomers should participate in the polymerization reaction of the cross-linking agent, i.e., the network structure formed by polymerization to generate a certain spatial structure suitable for the template molecule, and on the other hand, the functional monomers can generate specific recognition sites for the template molecule by the polymer through strong enough acting force between the functional monomers and the template molecule. However, because the polymer grid structure is difficult to deform, only the polymer formed by the functional monomer with the recognition group with smaller steric hindrance can allow the template molecule to enter the imprinting cavity of the polymer grid structure. The strong molecular action among host and guest molecules is mainly ionic bond and hydrogen bond, so that the selection of the current functional monomer is mainly simple small molecular polar compounds containing alkenyl and polar groups, such as acrylic acid, acrylamide, vinyl pyridine and the like.
Theoretically, the higher the specificity of the functional monomer to the template molecule, the stronger the specificity of the molecularly imprinted polymer to the recognition of the template molecule. Therefore, to increase the specificity of a functional monomer for a template molecule, it is necessary to use a functional monomer whose molecular structure more closely matches that of the template molecule. It is clear that such functional monomers are sterically more complex than simple polar groups and are therefore more sterically hindered. Therefore, to allow the template molecule to smoothly enter the imprinted cavity of the polymer, the lattice space of the polymer must be enlarged.
The chitosan oligosaccharide is called chitosan oligosaccharide and oligomeric chitosan, is an oligosaccharide product which is obtained by degrading chitosan and has the polymerization degree of 2-20 and is formed by beta-1,4 glycosidic bonds, the molecular weight is less than or equal to 3200Da, and the molecular structure is rich in hydroxyl and amino. Since the amino groups are uniformly distributed on both sides of the glucose unit, if a double bond can be introduced into the amino group, the resulting polymer has a larger lattice structure.
Due to the existence of a large number of polar groups in chitosan oligosaccharide molecules, the chitosan oligosaccharide molecules can be used as functional monomer oligomers in molecular imprinting materials, but due to the rigidity of the molecular structures, the chitosan oligosaccharide molecules are obviously difficult to form good matching with template molecules with specific structures, so that strong interaction occurs. In order to improve this situation, it is necessary to introduce a structure having flexibility into the molecular structure of the chitosan oligosaccharide.
In the process of recognizing antigen by antibody, the antibody effectively recognizes the corresponding part of the antigen by using the residue of the amino acid at the specific part. Therefore, if a specific amino acid unit can be introduced into the molecularly imprinted polymer and the flexibility of the residue is used to perform auxiliary recognition on the template molecule, the recognition performance of the molecularly imprinted polymer on the template molecule can be certainly improved. The construction of the functional monomer is not reported after retrieval.
Disclosure of Invention
Aiming at the defect that the molecular structure of a functional monomer in the existing molecular imprinting technology cannot be well matched with a template molecule, the invention provides a chitosan oligosaccharide derivative molecular imprinting functional monomer with a strong effect on curcumin molecules.
The chitosan oligosaccharide derivative molecular imprinting functional monomer is N- (N' -pentenoyl-amino acid acyl) -chitosan oligosaccharide.
The general formula of the molecular structure is as follows:
wherein n = 3-10, R is a side chain group of a neutral amino acid, which is asparagine, glutamine, methionine or threonine.
The curcumin molecular recognition molecule takes curcumin molecules as template molecules, chitosan oligosaccharide as a carrier and basic structural units of functional monomer oligomers as recognition molecules.
The formed small-segment peptide chain structure (-CONH-CH (R) -CONH-) also presents certain rigidity, and is crossed with a chitosan oligosaccharide molecular chain with a rigid structure in space, so that the shape of a grid structure is favorably kept (the shape cannot be deformed due to grid enlargement) after the cross-linking agent is cross-linked, the permeability of the imprinted material is favorably kept, more template molecules can enter, and the imprinted polymer can obtain more effective recognition sites.
The invention also aims to provide a method for preparing the chitosan oligosaccharide derivative molecular imprinting functional monomer.
The preparation method comprises the following steps:
1) Dissolving neutral amino acid and potassium carbonate in water, dropwise adding pentenoyl chloride under the condition of ice-water bath, and reacting at room temperature after dropwise adding to obtain an N-pentenoyl-amino acid solution; the neutral amino acid is asparagine, glutamine, methionine or threonine;
2) Adjusting the pH value of the N-pentenoyl-amino acid solution to be neutral, and mixing the solution with chitosan oligosaccharide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N-hydroxysuccinimide (NHS) for reaction to generate an N- (N' -pentenoyl-amino acid acyl) -chitosan oligosaccharide solution;
3) Dialyzing the reaction solution obtained in the step 2) by using a dialysis bag, and freeze-drying the dialyzate to obtain the N- (N' -pentenoyl-amino acid acyl) -chitosan oligosaccharide.
The reaction formula of the invention is as follows:
wherein n = 3-6,R is a side chain group of a neutral amino acid.
The invention has the advantages that:
(1) The pentenoyl is introduced into the amino group of the neutral amino acid, and the pentenoyl amino acid is coupled to the amino group of the chitosan oligosaccharide molecule, so that double bonds and flexible amino acid side chain groups can be simultaneously introduced into the chitosan oligosaccharide molecule, and the water solubility of the chitosan oligosaccharide cannot be greatly reduced due to the pentenoyl.
(2) The synthesis reaction is simple, the reaction condition is mild, the yield is high, and the reaction can be quantitative.
(3) The pentenoyl chloride is adopted as a reaction raw material, only two steps of reactions are needed, wherein the chitosan oligosaccharide coupling can be realized without separation after the first step of reaction, and the preparation cost can be greatly saved.
Furthermore, the charging molar ratio of the neutral amino acid and the pentenoyl chloride is 1: 1.05-1.10. Because of the higher activity of the acid chloride (which can react with water), the molar ratio of pentenoyl chloride in the present invention is suitably excessive in order to ensure that all of the amino acids can participate in the reaction.
Drawings
FIG. 1 is an infrared spectrum of N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide.
Fig. 2 is a comparison graph of cyclic voltammetry of a clean glassy carbon electrode, a molecularly imprinted electrode before curcumin elution, a molecularly imprinted electrode after curcumin elution, and a molecularly imprinted electrode after curcumin re-adsorption.
Fig. 3 is a graph showing the drop values of the cyclic voltammetry current responses of the molecularly imprinted electrode after curcumin elution to curcumin, tetrahydrocurcumin, ferulic acid, carotene and quercetin.
Detailed Description
1. Taking N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide as an example, the synthesis steps are as follows.
1. 0.125g (1.05 mmol) pentenoyl chloride was dissolved in 2mL dry N, N-Dimethylformamide (DMF) for use. Weighing 0.146g (1.0 mmol) of glutamine and 0.138g (1.0 mmol) of potassium carbonate, adding a proper amount of water for dissolving, cooling to 0 ℃ in an ice water bath, dropwise adding a DMF (dimethyl formamide) solution of pentenoyl chloride, and continuing the reaction for 1h after the completion to obtain the N-pentenoyl glutamine solution.
2. The pH of the N-pentenylglutamine solution was adjusted to neutral with 3N hydrochloric acid, and 0.17g of chitosan oligosaccharide (which may be dissolved in a small amount of water beforehand), 0.201g (1.05 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC), and 0.121g (1.05 mmol) of N-hydroxysuccinimide (NHS) were added and reacted at room temperature for 24 hours to obtain a reaction solution containing N- (N' -pentenylglutaminyl) -chitosan oligosaccharide.
3. Transferring the reaction solution into a dialysis bag with the cut-off molecular weight of 1000-2000 for dialysis, changing water once every 6h, and completing dialysis for 2 days. Freeze drying the dialyzate to obtain the N- (N' -pentenylglutaminyl) -chitosan oligosaccharide.
2. Characterization of the prepared N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide:
the obtained IR spectrum of N- (N' -pentenoyl-glutaminyl) -chitooligosaccharide is shown in FIG. 1.
In FIG. 1, at 3387cm -1 The nearby broad peaks are mainly O-H on hydroxyl group and N-H stretching vibration peak on amido group of chitosan oligosaccharide, 2928 cm -1 、2856 cm -1 Nearby absorption is the stretching vibration peak value of C-H bonds on methyl and methylene; 1655 cm -1 And 1561 cm -1 Mainly the stretching vibration peak of the amide group. 1072 cm -1 Mainly the absorption vibration peak of primary alcohol, secondary alcohol and tertiary alcohol hydroxyl.
3. And (4) analyzing and characterizing the elements of the target compound.
Through analysis and characterization, the mass percentage of each element is as follows:
c:49.1 percent; h:6.96 percent; n:10.54 percent; o:33.44 percent. The content of each element is basically consistent with the theoretical result.
The results of the infrared spectrogram and the element analysis show that: the method is adopted to obtain the N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide.
4. Application examples.
1. The preparation method of the curcumin electrochemical molecular imprinting sensor comprises the following steps:
3.16mg curcumin and 8.79mg N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide were added to 3mL solution of DMF and H in equal volume ratio 2 O, and then adding 50mg of cross-linking agent Ethylene Glycol Dimethacrylate (EGDMA) and 1mg of initiator ammonium persulfate. After standing for 5 hours, the mixture was purged with nitrogen gas for at least 10 minutes to remove dissolved oxygen, thereby obtaining a mixed solution.
3 mul of the mixed solution was dropped onto the surface of a clean glassy carbon electrode, which was covered with a clean cover glass. And then heating in a 60 ℃ oven for 10h, removing the cover glass, forming a layer of transparent polymer film on the surface of the glassy carbon electrode, and obtaining the molecularly imprinted electrode before curcumin elution.
And (3) eluting the molecularly imprinted electrode before curcumin elution for 50 minutes by using a mixed solution consisting of methanol and acetic acid in an equal volume ratio to obtain the molecularly imprinted electrode after curcumin elution, namely the curcumin electrochemical molecularly imprinted sensor.
2. Cyclic voltammetry curves of the curcumin molecularly imprinted membrane modified electrode in different states:
FIG. 2 shows that the clean glassy carbon electrode (control), the molecularly imprinted electrode before curcumin elution, the molecularly imprinted electrode after curcumin elution and the molecularly imprinted electrode after curcumin re-adsorption respectively contain 1.0 mMK 3 [Fe(CN) 6 ]10mL0.25M NaAc/HAc (pH 6.5) in water.
In addition, the method for obtaining the molecularly imprinted electrode after re-adsorbing curcumin comprises the following steps: soaking the molecular imprinting electrode eluted with the curcumin in a curcumin ethanol solution with the concentration of 0.2M to adsorb the curcumin till saturation.
Wherein curve a is a clean glassy carbon electrode containing 1.0 mMK 3 [Fe(CN) 6 ]10mL0.25M NaAc/HAc (pH 6.5) in water.
Curve b shows that the molecularly imprinted electrode after curcumin elution contains 1.0 mMK 3 [Fe(CN) 6 ]10mL0.25M NaAc/HAc (pH 6.5) in water.
Curve c shows that the molecularly imprinted electrode of curcumin before elution contains 1.0 mMK 3 [Fe(CN) 6 ]10mL0.25M NaAc/HAc (pH 6.5) in water.
Curve d shows that the molecular engram electrode after re-adsorbing curcumin contains 1.0 mMK 3 [Fe(CN) 6 ]10mL0.25M NaAc/HAc (pH 6.5) in water.
As can be seen from fig. 2: the response of the cyclic voltammetry current curve of the clean glassy carbon electrode is large (curve a), when the surface is covered with the molecularly imprinted membrane (namely, the molecularly imprinted membrane containing the template), the current response curve of the cyclic voltammetry is greatly reduced (curve c), and when the molecularly imprinted membrane containing the template is eluted, the current response of the cyclic voltammetry current is remarkably increased (curve b), and after the molecularly imprinted membrane of the template adsorbs curcumin again, the current response curve of the cyclic voltammetry current is reduced again (curve d).
3. The curcumin electrochemical molecular imprinting sensor is used for analyzing the cyclic voltammetry current response of curcumin and analogues thereof:
fig. 3 is a graph showing the drop values of the cyclic voltammetry current responses of the molecularly imprinted electrode (i.e. curcumin electrochemical molecularly imprinted sensor) after curcumin elution to curcumin and analogues thereof (tetrahydrocurcumin, ferulic acid, carotene, quercetin).
As can be seen from fig. 3, the electrode has the largest peak current drop of cyclic voltammetry of curcumin (i.e., greater adsorption to curcumin), and has smaller response to other analogues (and smaller adsorption to other analogues), so that the molecularly imprinted membrane has better selectivity.
In conclusion, it can be seen that: the N- (N' -pentenoyl-glutaminyl) -chitosan oligosaccharide can be used as a functional monomer oligomer for identifying curcumin, and can be used for determining the curcumin content in a sample solution.
Claims (3)
1. A chitosan oligosaccharide derivative molecular imprinting functional monomer is N- (N' -pentenoyl-amino acid acyl) -chitosan oligosaccharide, and has a molecular structure general formula as follows:
wherein n = 3-7,R is a side chain group of a neutral amino acid molecule, and the neutral amino acid is glutamine.
2. The method for preparing the molecularly imprinted functional monomer of the chitosan oligosaccharide derivative as claimed in claim 1, which comprises the steps of:
1) Dissolving neutral amino acid and potassium carbonate in water, dropwise adding pentenoyl chloride under the condition of ice-water bath, and then placing at room temperature for reaction to prepare an N-pentenoyl-amino acid solution; the neutral amino acid is glutamine;
2) Adjusting the pH value of the N-pentenoyl-amino acid solution to be neutral, and then mixing the solution with chitosan oligosaccharide, 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N-hydroxysuccinimide for reaction to generate an N- (N' -pentenoyl-amino acid acyl) -chitosan oligosaccharide solution;
3) Dialyzing the reaction solution obtained in the step 2) by using a dialysis bag, and freeze-drying the dialyzate to obtain the N- (N' -pentenoyl-amino acid acyl) -chitosan oligosaccharide.
3. The method for preparing the chitosan oligosaccharide derivative molecular imprinting functional monomer according to claim 2, wherein the feeding molar ratio of the neutral amino acid to the pentenoyl chloride is 1: 1.05-1.10.
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| US6582971B1 (en) * | 2000-08-21 | 2003-06-24 | Lynntech, Inc. | Imprinting large molecular weight compounds in polymer composites |
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| CN106967183A (en) * | 2017-04-06 | 2017-07-21 | 扬州工业职业技术学院 | N‑（N ' oleoyl glycyl）Chitosan oligosaccharide sodium sulfonate and preparation method thereof |
| CN107081110A (en) * | 2017-04-06 | 2017-08-22 | 扬州大学 | A kind of partially grafted chitosan oligosaccharide surfactant and preparation method |
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| US6582971B1 (en) * | 2000-08-21 | 2003-06-24 | Lynntech, Inc. | Imprinting large molecular weight compounds in polymer composites |
| CN101381430A (en) * | 2008-10-09 | 2009-03-11 | 浙江工业大学 | Molecule brand polymer of curcumin, preparation method and application thereof |
| CN105601846A (en) * | 2015-09-10 | 2016-05-25 | 河北科技师范学院 | Chitosan surface molecularly imprinted rod-like material |
| CN106967183A (en) * | 2017-04-06 | 2017-07-21 | 扬州工业职业技术学院 | N‑（N ' oleoyl glycyl）Chitosan oligosaccharide sodium sulfonate and preparation method thereof |
| CN107081110A (en) * | 2017-04-06 | 2017-08-22 | 扬州大学 | A kind of partially grafted chitosan oligosaccharide surfactant and preparation method |
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