CN111318237B - Collagen-chitosan hydrogel and preparation method thereof - Google Patents
Collagen-chitosan hydrogel and preparation method thereof Download PDFInfo
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- CN111318237B CN111318237B CN202010202330.4A CN202010202330A CN111318237B CN 111318237 B CN111318237 B CN 111318237B CN 202010202330 A CN202010202330 A CN 202010202330A CN 111318237 B CN111318237 B CN 111318237B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0052—Preparation of gels
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Abstract
The invention discloses a collagen-chitosan hydrogel and a preparation method thereof, wherein the preparation method comprises the following steps: inserting a cathode and an anode connected with an electrochemical workstation into a mixed solution of collagen and chitosan; then, controlling a power-on mode through an electrochemical workstation to carry out electrodeposition so as to obtain the collagen-chitosan hydrogel; wherein the pH value of the mixed solution of the collagen and the chitosan is not less than 5. The preparation method of the invention is environment-friendly, mild in reaction condition and free from damage to the biological activity of collagen and chitosan.
Description
Technical Field
The invention belongs to the technical field of biological materials, and particularly relates to a collagen-chitosan hydrogel and a preparation method thereof.
Background
The collagen, collagen for short, is a structural protein widely existing in the bodies of vertebrates, three peptide chains are wound to form a triple helix structure, the molecular chain length is about 300nm, the diameter is about 1.5nm, and the molecular weight is about 300 kDa. Collagen is an important component of tissues such as skin, bones and the like, so the collagen-based biomaterial has the excellent characteristics of good biocompatibility, low immunogenicity, degradability, absorbability and the like. However, although collagen extracted from living bodies has self-assembly bioactivity, the mechanical properties and gelling ability of collagen hydrogel are far from those of collagen in living bodies. Although researchers improve the performance of the modified polyester resin by crosslinking, modifying and the like, the residual toxic crosslinking agent, the loss of the bioactivity of the modified product, the toxicity and the compatibility still hinder the further practical application of the modified polyester resin. Meanwhile, the current method for modifying the hollow structure of the collagen is complex to operate, and can cause the reduction of the compatibility and the bioactivity of the collagen.
Chitosan (chitosan) is obtained by deacetylation of chitin (chitin) widely existing in nature, and has a chemical name of polyglucosamine (1-4) -2-amino-B-D glucose. Chitosan is the only polycation mucopolysaccharide in nature and has the properties of multiple electrolytes. Due to intermolecular hydrogen bonding, the acidic aqueous solution of chitosan has certain viscosity and can immediately become gel when encountering an alkaline reagent, however, compared with collagen, the chitosan hydrogel is easily influenced by the pH value of the environment, the gel strength is not high, and the swelling degree in water is not large; and chitosan is less biocompatible than collagen.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of collagen-chitosan hydrogel, so that the prepared collagen-chitosan hydrogel has a hollow tubular structure and has good biocompatibility and bioactivity.
In order to accomplish the above objects, an aspect of the present invention provides a method for preparing a collagen-chitosan hydrogel, the method comprising: inserting a cathode and an anode connected with an electrochemical workstation into a mixed solution of collagen and chitosan; then, controlling an electrifying mode through an electrochemical workstation to carry out electrodeposition to obtain the collagen-chitosan hydrogel; wherein the pH value of the mixed solution of the collagen and the chitosan is not less than 5.
In another aspect of the present invention, there is provided a collagen-chitosan hydrogel prepared by the above-mentioned preparation method.
The technical scheme of the invention has the following beneficial effects:
(1) the preparation method is simple and easy to operate, and the diameter and the shape of the hollow part of the gel fiber can be controlled by changing the diameter and the cross section shape of the stainless steel needle;
(2) the preparation method is environment-friendly, mild in reaction conditions and free of damage to the biological activity of collagen and chitosan;
(3) the hollow collagen-chitosan hydrogel prepared by the invention has a complex internal structure and a large specific surface area, and can be used as a good carrier of a medicament to be applied to the fields of medicament-carrying slow release, tissue engineering and the like;
(4) the method can accurately control the thickness and the component content of the collagen-chitosan gel, and discloses a novel method for accurately controlling the space, time and quantification of soft substances;
(5) the invention can be applied to the fields of bioengineering, tissue engineering, food processing, spinning, medicine, environmental protection and the like.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings, in which like reference numerals generally represent like parts throughout.
Figure 1 shows a schematic cross-sectional view of a collagen-chitosan hydrogel according to the present invention.
Figure 2 shows a schematic side view of a collagen-chitosan hydrogel according to the present invention.
Figure 3 shows a photomicrograph of a collagen-chitosan hydrogel according to one embodiment of the present invention.
Figure 4 shows an optical microscope image of a collagen-chitosan hydrogel according to one embodiment of the present invention. Wherein the scale in the figure is 1000 μm, and 1.38mm, 1.70mm and 2.12mm in the figure represent the diameters of the collagen-chitosan hydrogel, respectively.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
One aspect of the present invention provides a method for preparing a collagen-chitosan hydrogel, the method comprising: inserting a cathode and an anode connected with an electrochemical workstation into a mixed solution of collagen and chitosan; then, controlling an electrifying mode through an electrochemical workstation to carry out electrodeposition to obtain the collagen-chitosan hydrogel; wherein the pH value of the mixed solution of the collagen and the chitosan is not less than 5.
The invention utilizes the characteristic that both chitosan and collagen can be dissolved in dilute acid aqueous solution to prepare collagen-chitosan hydrogel by an electrochemical method, and the prepared collagen-chitosan hydrogel has a hollow inner cavity and is hollow collagen-chitosan hydrogel. The method has the advantages of simple and rapid preparation, no pollution and the like, does not change the components of the original solution, can accurately control the thickness of the gel through an electric signal, utilizes the pH stimulation responsiveness of chitosan amino to apply the electric signal to a cathode to guide the in-situ deposition of the chitosan, and accurately controls the thickness by utilizing the transfer of the electric quantity (Q ═ idt). Discloses a method for inducing a soft substance to generate an accurate complex structure through an electric signal password, which can be applied to the fields of bioengineering, tissue engineering, food processing, spinning, medicine, environmental protection and the like.
The collagen-chitosan hydrogel of the present invention has a hollow inner cavity, and the structure thereof is shown in fig. 1 and 2.
In the invention, the diameter and the shape of the hollow part of the hydrogel can be controlled by changing the diameter and the cross section shape of the stainless steel needle; the hollow inner diameter of the hollow tubular hydrogel is the diameter of the stainless steel needle, and the overall shape and the cross section shape of the hollow inner cavity of the hollow tubular hydrogel can be changed according to the shape of the electrode.
In the present invention, by changing the electrical signal parameters, such as: current, voltage, time, etc., hollow tubular hydrogels of different thicknesses can be obtained.
When the natural polymer hydrogel is formed, usually, irradiation with light or addition of a cross-linking agent is required, so that the structure of chitosan itself is sometimes damaged, and toxic substances are even introduced, thereby limiting the application range of the natural polymer hydrogel. However, the method for preparing the hydrogel by adopting the electrodeposition method is convenient and quick, has no pollution, and has no damage to the structures and biological activities of collagen and chitosan.
According to the present invention, preferably, the mixed solution of collagen and chitosan is prepared by the following method: mixing the collagen and the chitosan with water, then adding hydrochloric acid to completely dissolve the collagen and the chitosan, and finally adjusting the pH value of the mixed solution to be not less than 5 by using NaOH.
According to the present invention, preferably, the mixed solution of collagen and chitosan is prepared by the following method:
(1) mixing chitosan and water, then adding hydrochloric acid to completely dissolve the chitosan, and finally adjusting the pH value of the solution to be not less than 5 by using NaOH to obtain a chitosan solution;
(2) mixing collagen and water, adding hydrochloric acid to completely dissolve the collagen, and finally adjusting the pH value of the solution to be not less than 5 by using NaOH to obtain a collagen solution;
(3) and mixing the chitosan solution and the collagen solution to obtain a mixed solution of the collagen and the chitosan.
In the invention, the concentration of the chitosan solution in the step (1) is 5-20 mg/mL; the concentration of the collagen solution in the step (2) is 1-10 mg/mL.
In the invention, the mass concentration of the hydrochloric acid is 30-40%.
According to the invention, preferably, the cathode is a stainless steel needle and the anode is a Pt wire.
According to the present invention, preferably, the energization mode is a constant current mode.
According to the present invention, preferably, the operating current of the constant current mode is 0.3mA to 1 mA.
In the invention, the power-on mode can also be a constant voltage mode or a rated coulomb mode; wherein the working voltage of the constant voltage mode is 0.1V-15V.
According to the invention, the electrodeposition time is preferably between 5s and 90 s.
According to the present invention, preferably, the mass ratio of collagen to chitosan in the mixed solution of collagen and chitosan is (0 to 0.25): 1, and the mass ratio of the collagen to the chitosan in the mixed solution of the collagen and the chitosan is not 0.
Another aspect of the present invention provides a collagen-chitosan hydrogel prepared by the above preparation method.
The invention is further illustrated by the following examples:
the reagents used in the following examples are all analytical grade reagents.
Example 1
The embodiment provides a preparation method of collagen-chitosan hydrogel, which specifically comprises the following steps:
(1) adding 0.20g of chitosan into 10mL of deionized water, stirring at room temperature of 25 ℃, adding 0.27mL of concentrated hydrochloric acid with the mass concentration of 36% to completely dissolve the chitosan, and finally adjusting the pH value of the solution to be 5 by using NaOH to obtain a chitosan solution with the concentration of 20 mg/mL;
(2) adding 0.02g of collagen (collagen) into 10mL of deionized water, stirring in a low-temperature operation table at 4 ℃, adding 0.27mL of concentrated hydrochloric acid with the mass concentration of 36% to completely dissolve the collagen, and finally adjusting the pH value of the solution to be 5 by using NaOH to obtain a collagen solution with the concentration of 2 mg/mL;
(3) and mixing 10ml of the chitosan solution and 10ml of the collagen solution to obtain a mixed solution of the collagen and the chitosan.
(4) Inserting a cathode and an anode connected to an electrochemical workstation into the mixed solution of collagen and chitosan; then, controlling an electrifying mode through an electrochemical workstation to carry out electrodeposition to obtain the collagen-chitosan hydrogel; wherein, a Pt metal wire is used as an anode, a stainless steel needle with the radius of 0.2mm is used as a cathode, an electrifying mode is a constant current working mode, the working current is 0.5mA, and the deposition time is 30s or 45s or 60 s. The hydrogel prepared when the deposition time was 30s was as shown in fig. 3 and fig. 4 (a), the hydrogel prepared when the deposition time was 45s was as shown in fig. 4 (b), and the hydrogel prepared when the deposition time was 60s was as shown in fig. 4 (c).
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (6)
1. A preparation method of collagen-chitosan hydrogel is characterized by comprising the following steps: inserting a cathode and an anode connected with an electrochemical workstation into a mixed solution of collagen and chitosan; then, controlling an electrifying mode through an electrochemical workstation to carry out electrodeposition to obtain the collagen-chitosan hydrogel; wherein the pH value of the mixed solution of the collagen and the chitosan is not less than 5;
the mixed solution of collagen and chitosan is prepared by the following method:
(1) mixing chitosan and water, then adding hydrochloric acid to completely dissolve the chitosan, and finally adjusting the pH value of the solution to be not less than 5 by using NaOH to obtain a chitosan solution;
(2) mixing collagen and water, adding hydrochloric acid to completely dissolve the collagen, and finally adjusting the pH value of the solution to be not less than 5 by using NaOH to obtain a collagen solution;
(3) mixing the chitosan solution and the collagen solution to obtain a mixed solution of collagen and chitosan;
the deposition time of the electrodeposition is 5 s-90 s.
2. The method of claim 1, wherein the cathode is a stainless steel needle and the anode is a Pt wire.
3. The production method according to claim 1, wherein the energization mode is a constant current mode.
4. The production method according to claim 3, wherein the operating current in the galvanostatic mode is 0.3mA to 1 mA.
5. The method according to claim 1, wherein the mass ratio of collagen to chitosan in the mixed solution of collagen and chitosan is (0 to 0.25): 1, and the mass ratio of the collagen to the chitosan in the mixed solution of the collagen and the chitosan is not 0.
6. A collagen-chitosan hydrogel prepared by the preparation method of any one of claims 1 to 5.
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| CN103614756A (en) * | 2013-11-15 | 2014-03-05 | 武汉大学 | Method for preparing hollow multi-layer chitosan hydrogel |
| CN106622153A (en) * | 2016-11-23 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of collagen/chitosan imprinted material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5529914A (en) * | 1990-10-15 | 1996-06-25 | The Board Of Regents The Univeristy Of Texas System | Gels for encapsulation of biological materials |
| US7883615B2 (en) * | 2003-02-12 | 2011-02-08 | University Of Maryland, College Park | Controlled electrochemical deposition of polysaccharide films and hydrogels, and materials formed therefrom |
| US8663988B2 (en) * | 2011-12-09 | 2014-03-04 | Medtrain Technologies, Llc | Thermally induced gelation of collagen hydrogel and method of thermally inducing gelling a collagen hydrogel |
| WO2016098057A1 (en) * | 2014-12-17 | 2016-06-23 | Socovar, L.P. | Chitosan-based hydrogel and applications thereof |
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| CN102641727A (en) * | 2012-04-25 | 2012-08-22 | 大连中汇达科学仪器有限公司 | Chitosan collagen biological adsorbent prepared based on ionic liquid serving as solvent |
| CN103614756A (en) * | 2013-11-15 | 2014-03-05 | 武汉大学 | Method for preparing hollow multi-layer chitosan hydrogel |
| CN106622153A (en) * | 2016-11-23 | 2017-05-10 | 辽宁石油化工大学 | Preparation method of collagen/chitosan imprinted material |
| CN110343169A (en) * | 2019-08-12 | 2019-10-18 | 武汉轻工大学 | A kind of modified I-type collagen and method of modifying and collagen gel using modification I-type collagen preparation |
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