CN115010979A - High-strength chitosan/sodium alginate ion imprinted gel membrane and preparation method thereof - Google Patents

High-strength chitosan/sodium alginate ion imprinted gel membrane and preparation method thereof Download PDF

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CN115010979A
CN115010979A CN202210759736.1A CN202210759736A CN115010979A CN 115010979 A CN115010979 A CN 115010979A CN 202210759736 A CN202210759736 A CN 202210759736A CN 115010979 A CN115010979 A CN 115010979A
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chitosan
sodium alginate
ion imprinted
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gel membrane
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CN115010979B (en
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鲍艳
郑茜
郭茹月
刘超
张文博
祝茜
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Shaanxi University of Science and Technology
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Abstract

The invention provides a high-strength chitosan/sodium alginate ion imprinted gel membrane and a preparation method thereof, belongs to the technical field of biological materials and hydrogel preparation, and solves the technical problems of poor mechanical property and poor selectivity in the preparation of chitosan/sodium alginate ion imprinted gel membranes in the prior art. The preparation method disclosed by the invention has the advantages that the chitosan and the sodium alginate are dissolved in the alkaline solution, the chitosan forms a rigid nano fiber structure arranged in parallel in the alkaline solution, and simultaneously, the chitosan and the flexible sodium alginate molecular chain generate an entanglement effect, so that the mechanical strength of the chitosan/sodium alginate ion imprinted gel membrane is effectively improved; and then placing the chitosan/sodium alginate pre-gel solution in a cadmium nitrate mixed solution for gelation, wherein stable cage-shaped molecules can be formed in the gel in the gelation process.

Description

High-strength chitosan/sodium alginate ion imprinted gel membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of biological materials and hydrogel preparation, and particularly relates to a high-strength chitosan/sodium alginate ion imprinted gel membrane and a preparation method thereof.
Background
The ion imprinting technology is derived from the molecular imprinting technology, can realize high-capacity selective adsorption and high-sensitivity detection on specifically existing free-state or combined-state metal ions in a complex environment, has the advantages of special-effect identification, simple preparation process, simplicity and convenience in operation and the like, and has wide application prospects in the aspects of heavy metal ion detection, solid-phase extraction, sensors and the like. The ion imprinting hydrogel is a functional hydrogel with specific response to target ions, which is obtained by applying an ion imprinting technology to hydrogel preparation. Compared with the common hydrogel, the crosslinking degree of the ion imprinting hydrogel is changed in space, and the change enables the hydrogel to have proper rigidity and an effective local imprinting structure when detecting and adsorbing metal ions, so that the imprinting effect of the hydrogel is improved. However, the currently prepared ion imprinted hydrogel adopts methacrylic acid, pyrrole, phenol and derivatives thereof as functional monomers, has certain toxicity to the environment, is too high in cost and complex in preparation process, and limits the application range of the ion imprinted hydrogel.
The natural polysaccharide is cheap and easily available, is easy to degrade, and is rich in various active functional groups (-OH, -NH) 2 -COOH) in a biomass material. Natural prints based on polysaccharide materials due to multiple interactions between their reactive functional groups and metal ionsThe hydrogel can show good imprinting effect in a complex environment, however, the strength of the hydrogel prepared by the natural polysaccharide is too low at present, so that the imprinting cavity of the hydrogel imprinting material based on the natural polysaccharide is easy to break during the use process, and the imprinting effect is lower. Although the addition of the chemical crosslinking agent improves the strength of the hydrogel to some extent, the addition of the chemical crosslinking agent has toxicity and may cause environmental pollution.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high-strength chitosan/sodium alginate ion imprinted gel membrane and a preparation method thereof, which are used for solving the technical problems of poor mechanical property and poor selectivity in the preparation of the chitosan/sodium alginate ion imprinted gel membrane in the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme to realize the purpose:
the invention discloses a preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane, which comprises the following steps:
s1: dissolving chitosan and sodium alginate in an alkaline solution to obtain a chitosan/sodium alginate pre-gel solution;
s2: injecting the chitosan/sodium alginate pre-gel solution into a mold, and then placing the mold into a cadmium nitrate mixed solution for gelation to obtain a chitosan/sodium alginate gel film;
s3: and soaking the chitosan/sodium alginate gel membrane in an eluent for elution, and then washing to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
Further, in S1, the mass ratio of the chitosan to the sodium alginate is (5-9): (1-5); the mass concentration of the chitosan/sodium alginate pre-gel solution is 4-8 wt%; the deacetylation degree of the chitosan is 70-85%; the temperature for dissolving the chitosan and the sodium alginate in the alkaline solution is-10 ℃ to 20 ℃, and the dissolving time is 6h to 12 h.
Further, in S1, the alkaline solution is a mixed solution of alkali, urea and water, wherein the alkali is potassium hydroxide or lithium hydroxide; in the alkaline solution, the mass concentration of alkali is 4 wt% -12 wt%, and the mass concentration of urea is 7 wt% -14 wt%.
Further, in S2, the cadmium nitrate mixed solution is obtained by mixing cadmium nitrate, glacial acetic acid, and absolute ethyl alcohol, wherein the mass concentration of cadmium nitrate in the cadmium nitrate mixed solution is 4 wt% to 7 wt%, and the mass concentration of glacial acetic acid is 6 wt% to 10 wt%.
Further, in S2, the time for gelation is 0.3 to 1 hour; step 2 is carried out at room temperature.
Further, in S3, the eluent is an aqueous solution of disodium ethylenediaminetetraacetate; the concentration of the water solution of the ethylene diamine tetraacetic acid is 0.1-0.5 mol/L.
Further, in S3, the elution time is 3 to 6 hours; the washing is carried out by adopting pure water; the S3 is performed at room temperature.
The invention also discloses the high-strength chitosan/sodium alginate ion imprinted gel membrane prepared by the preparation method, wherein the tensile strength of the high-strength chitosan/sodium alginate ion imprinted gel membrane is 1.26 MPa-1.6 MPa, and the imprinting factor is 2.64.
Compared with the prior art, the invention has the following beneficial effects:
the invention discloses a preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane, which is characterized in that chitosan and sodium alginate are dissolved in alkaline solution, a rigid nanofiber structure arranged in parallel is formed in the alkaline solution by utilizing the chitosan, and meanwhile, entanglement is generated between molecular chains of the chitosan and flexible sodium alginate, so that the mechanical strength of the chitosan/sodium alginate ion imprinted gel membrane is effectively improved; then placing the chitosan/sodium alginate pre-gel solution into a cadmium nitrate mixed solution for gelation, wherein in the gelation process, chitosan and sodium alginate are used as functional monomers, and a large number of active functional groups (-NH) are contained on the molecules of the chitosan and sodium alginate 2 、-OH、-CH 2 The stronger binding capacity between OH, -COOH) and the template ions Cd (II) can form stable cage-shaped molecules in gel, and the binding capacity of the gel is higher than that of Cd (II)Removing, wherein a three-dimensional imprinting cavity structure which is complementary with Cd (II) is formed on the surface and inside of the gel, and the three-dimensional imprinting cavity structure has the specific recognition capability similar to that of an antibody and an antigen, so that the specific detection of Cd (II) is realized; the preparation method of the invention does not use any cross-linking agent, does not need toxic solvent and special equipment, and has the advantages of simple operation, low cost, environmental protection and wide application prospect.
The invention also discloses the high-strength chitosan/sodium alginate ion imprinted gel membrane prepared by the method, and the high-strength chitosan/sodium alginate ion imprinted gel membrane is proved to have the tensile strength of 1.26MPa to 1.6MPa, the imprinting factor of 2.64 and good strength and ion imprinting effect according to related experimental results.
Drawings
FIG. 1 is a mechanical characterization diagram before and after Cd removal of a high-strength chitosan/sodium alginate ion imprinted gel;
wherein: 1-before Cd (II) removal; 2-after Cd (II) removal;
FIG. 2 is a schematic diagram showing the selectivity and adsorption effect on Cd (II) before and after high-strength chitosan/sodium alginate ion imprinted gel imprinting;
wherein 1 to 8 each represents Cr 3+ 、Mn 2+ 、Cd 2+ 、Ni 2+ 、Cu 2+ 、Ca 2+ 、Mg 2+ 、Ba 2+ 。
Detailed Description
To make the features and effects of the present invention comprehensible to those skilled in the art, general description and definitions are made below with reference to terms and expressions mentioned in the specification and claims. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
The theory or mechanism described and disclosed herein, whether correct or incorrect, should not limit the scope of the present invention in any way, i.e., the present disclosure may be practiced without limitation to any particular theory or mechanism.
All features defined herein as numerical ranges or percentage ranges, such as values, amounts, levels and concentrations, are for brevity and convenience only. Accordingly, the description of numerical ranges or percentage ranges should be considered to cover and specifically disclose all possible subranges and individual numerical values (including integers and fractions) within the range.
Unless otherwise specified herein, "comprising," including, "" containing, "" having, "or the like, means" consisting of … … "and" consisting essentially of … …, "e.g.," a comprises a "means" a comprises a and the other, "and" a comprises a only.
In this context, for the sake of brevity, not all possible combinations of features in the various embodiments or examples are described. Therefore, the respective features in the respective embodiments or examples may be arbitrarily combined as long as there is no contradiction between the combinations of the features, and all the possible combinations should be considered as the scope of the present specification.
The invention provides a preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane, which comprises the following steps:
step 1, dissolving chitosan with deacetylation degree of 70-85% and sodium alginate in an alkaline mixed solution composed of alkali, urea and water at-10 ℃ to obtain a chitosan/sodium alginate pre-gel solution. Wherein the mass ratio of the chitosan to the sodium alginate is 9-5: 1-5; the alkali is potassium hydroxide or lithium hydroxide; the concentration of alkali in the alkaline solution is 4-12 wt%, and the concentration of urea is 7-14 wt%; the dissolving time is 6-12 h; the concentration of the pre-gel solution is 4-8 wt%.
And 2, injecting the chitosan/sodium alginate pre-gel solution into a mold at 25 ℃, and then placing the mold into a mixed solution of cadmium nitrate, glacial acetic acid and absolute ethyl alcohol for gelation to obtain the chitosan/sodium alginate gel film. Wherein the concentration of cadmium nitrate in the mixed solution is 4-7 wt%, and the concentration of glacial acetic acid is 6-10 wt%; the gel time is 0.3-1 h.
And 3, soaking the chitosan/sodium alginate gel membrane in 0.1-0.5 mol/L disodium ethylene diamine tetraacetate aqueous solution at 25 ℃ to elute for 3-6 hours, and then washing with pure water to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
The following examples use instrumentation conventional in the art. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers. The various starting materials used in the examples which follow, unless otherwise indicated, are conventional commercial products having specifications which are conventional in the art. In the description of the present invention and the following examples, "%" represents weight percent, "parts" represents parts by weight, and proportions represent weight ratios, unless otherwise specified.
Example 1
A preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane comprises the following steps:
step 1: dissolving chitosan with deacetylation degree of 70% and sodium alginate in an alkaline mixed solution composed of lithium hydroxide, urea and water at-10 deg.C for 6h to obtain 4 wt% chitosan/sodium alginate pre-gel solution; wherein the mass ratio of the chitosan to the sodium alginate is 9:1, the mass concentration of the lithium hydroxide in the alkaline solution is 4 wt%, and the mass concentration of the urea is 7 wt%;
step 2: injecting the chitosan/sodium alginate pre-gel solution into a mould at 25 ℃, and then placing the mould into a mixed solution consisting of cadmium nitrate, glacial acetic acid and absolute ethyl alcohol for gelation for 0.3h to obtain a chitosan/sodium alginate gel film; wherein the mass concentration of cadmium nitrate in the cadmium nitrate mixed solution is 4 wt%, and the concentration of glacial acetic acid is 6 wt%;
s3: soaking the chitosan/sodium alginate gel membrane in 0.1mol/L disodium ethylene diamine tetraacetate aqueous solution at 25 ℃ for eluting for 3 hours, and then washing with pure water to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
Example 2
A preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane comprises the following steps:
step 1: dissolving chitosan with deacetylation degree of 70% and sodium alginate in an alkaline mixed solution composed of lithium hydroxide, urea and water at-10 deg.C for 8h to obtain 5 wt% chitosan/sodium alginate pre-gel solution; wherein the mass ratio of the chitosan to the sodium alginate is 8:2, the mass concentration of the lithium hydroxide in the alkaline solution is 6 wt%, and the mass concentration of the urea is 10 wt%;
step 2: injecting the chitosan/sodium alginate pre-gel solution into a mould at 25 ℃, and then placing the mould into a mixed solution consisting of cadmium nitrate, glacial acetic acid and absolute ethyl alcohol for gelation for 0.3h to obtain a chitosan/sodium alginate gel film; wherein the mass concentration of cadmium nitrate in the cadmium nitrate mixed solution is 4 wt%, and the concentration of glacial acetic acid is 7 wt%;
s3: and (2) soaking the chitosan/sodium alginate gel membrane in 0.2mol/L disodium ethylene diamine tetraacetate aqueous solution at 25 ℃ for eluting for 4 hours, and then washing with pure water to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
Example 3
A preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane comprises the following steps:
step 1: dissolving chitosan with deacetylation degree of 80% and sodium alginate in an alkaline mixed solution composed of lithium hydroxide, urea and water at-10 deg.C for 8h to obtain 6 wt% chitosan/sodium alginate pre-gel solution; wherein the mass ratio of the chitosan to the sodium alginate is 7:3, the mass concentration of the lithium hydroxide in the alkaline solution is 8 wt%, and the mass concentration of the urea is 12 wt%;
step 2: injecting the chitosan/sodium alginate pre-gel solution into a mould at 25 ℃, and then placing the mould into a mixed solution consisting of cadmium nitrate, glacial acetic acid and absolute ethyl alcohol for gelation for 0.6h to obtain a chitosan/sodium alginate gel film; wherein the mass concentration of cadmium nitrate in the cadmium nitrate mixed solution is 5 wt%, and the concentration of glacial acetic acid is 9 wt%;
s3: and (2) soaking the chitosan/sodium alginate gel membrane in 0.3mol/L disodium ethylene diamine tetraacetate aqueous solution at 25 ℃ for eluting for 5 hours, and then washing with pure water to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
Example 4
A preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane comprises the following steps:
step 1: dissolving chitosan with deacetylation degree of 80% and sodium alginate in an alkaline mixed solution composed of lithium hydroxide, urea and water at-10 deg.C for 10h to obtain 7 wt% chitosan/sodium alginate pre-gel solution; wherein the mass ratio of the chitosan to the sodium alginate is 6:4, the mass concentration of the lithium hydroxide in the alkaline solution is 10 wt%, and the mass concentration of the urea is 9 wt%;
step 2: injecting the chitosan/sodium alginate pre-gel solution into a mold at 25 ℃, and then placing the mold into a mixed solution composed of cadmium nitrate, glacial acetic acid and absolute ethyl alcohol for gelling for 0.9h to obtain a chitosan/sodium alginate gel film; wherein the mass concentration of cadmium nitrate in the cadmium nitrate mixed solution is 6 wt%, and the concentration of glacial acetic acid is 8 wt%;
s3: and (2) soaking the chitosan/sodium alginate gel membrane in 0.5mol/L disodium ethylene diamine tetraacetate aqueous solution at 25 ℃ for eluting for 4 hours, and then washing with pure water to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
Example 5
A preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane comprises the following steps:
step 1: dissolving chitosan with deacetylation degree of 85% and sodium alginate in an alkaline mixed solution composed of lithium hydroxide, urea and water at-10 deg.C for 12h to obtain 8 wt% chitosan/sodium alginate pre-gel solution; wherein the mass ratio of the chitosan to the sodium alginate is 5:5, the mass concentration of the lithium hydroxide in the alkaline solution is 12 wt%, and the mass concentration of the urea is 14 wt%;
step 2: injecting the chitosan/sodium alginate pre-gel solution into a mould at 25 ℃, and then placing the mould into a mixed solution consisting of cadmium nitrate, glacial acetic acid and absolute ethyl alcohol for gelling for 1h to obtain a chitosan/sodium alginate gel film; wherein the mass concentration of cadmium nitrate in the cadmium nitrate mixed solution is 7 wt%, and the concentration of glacial acetic acid is 10 wt%;
s3: and (2) soaking the chitosan/sodium alginate gel membrane in 0.4mol/L disodium ethylene diamine tetraacetate aqueous solution at 25 ℃ for eluting for 6 hours, and then washing with pure water to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
FIG. 1 is a mechanical representation diagram before and after Cd removal of high-strength chitosan/sodium alginate ion imprinted gel, and the diagram shows that the mechanical property of the chitosan/sodium alginate ion imprinted gel membrane after Cd (II) elution is greatly improved compared with that of the chitosan/sodium alginate gel membrane, and the ionic imprinted site formed after Cd (II) removal is helpful for improving the mechanical property of the gel membrane.
FIG. 2 shows the selectivity and adsorption effect of the chitosan/sodium alginate ion imprinted gel membrane prepared by the method on Cd (II), and the chitosan/sodium alginate ion imprinted gel membrane prepared by the method has good adsorption effect and selectivity on Cd (II), the adsorption capacity can reach 79mg/g, and the imprinting factor is 2.64.
The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.

Claims (8)

1. A preparation method of a high-strength chitosan/sodium alginate ion imprinted gel membrane is characterized by comprising the following steps:
s1: dissolving chitosan and sodium alginate in an alkaline solution to obtain a chitosan/sodium alginate pre-gel solution;
s2: injecting the chitosan/sodium alginate pre-gel solution into a mold, and then placing the mold into a cadmium nitrate mixed solution for gelation to obtain a chitosan/sodium alginate gel film;
s3: and soaking the chitosan/sodium alginate gel membrane in an eluent for elution, and then washing to obtain the high-strength chitosan/sodium alginate ion imprinted gel membrane.
2. The preparation method of the high-strength chitosan/sodium alginate ion imprinted gel membrane as claimed in claim 1, wherein in S1, the mass ratio of chitosan to sodium alginate is (5-9): (1-5); the mass concentration of the chitosan/sodium alginate pre-gel solution is 4-8 wt%; the deacetylation degree of the chitosan is 70-85%; the temperature for dissolving the chitosan and the sodium alginate in the alkaline solution is-10 ℃ to 20 ℃, and the dissolving time is 6h to 12 h.
3. The method for preparing a high-strength chitosan/sodium alginate ion imprinted gel membrane as claimed in claim 1, wherein in S1, the alkaline solution is a mixed solution of alkali, urea and water, wherein the alkali is potassium hydroxide or lithium hydroxide; in the alkaline solution, the mass concentration of alkali is 4 wt% -12 wt%, and the mass concentration of urea is 7 wt% -14 wt%.
4. The preparation method of the high-strength chitosan/sodium alginate ion imprinted gel membrane as claimed in claim 1, wherein in S2, the cadmium nitrate mixed solution is obtained by mixing cadmium nitrate, glacial acetic acid and absolute ethyl alcohol, the mass concentration of cadmium nitrate in the cadmium nitrate mixed solution is 4 wt% -7 wt%, and the mass concentration of glacial acetic acid is 6 wt% -10 wt%.
5. The method for preparing a high-strength chitosan/sodium alginate ion imprinted gel membrane as claimed in claim 1, wherein in S2, the time for gelation is 0.3 h-1 h; step 2 is carried out at room temperature.
6. The method for preparing a high-strength chitosan/sodium alginate ion imprinted gel membrane as claimed in claim 1, wherein in S3, the eluent is an aqueous solution of disodium ethylenediaminetetraacetate; the concentration of the water solution of the ethylene diamine tetraacetic acid is 0.1-0.5 mol/L.
7. The method for preparing a high-strength chitosan/sodium alginate ion imprinted gel membrane as claimed in claim 1, wherein in S3, the elution time is 3-6 h; the washing is carried out by adopting pure water; the S3 is performed at room temperature.
8. The high-strength chitosan/sodium alginate ion imprinted gel membrane prepared by the preparation method of the high-strength chitosan/sodium alginate ion imprinted gel membrane as claimed in any one of claims 1 to 7 is characterized in that the tensile strength of the high-strength chitosan/sodium alginate ion imprinted gel membrane is 1.26MPa to 1.6MPa, and the imprinting factor is 2.64.
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