CN109180970A - A kind of citric acid cross-linked chitosan and the hydrogel of dopamine and preparation method thereof - Google Patents

A kind of citric acid cross-linked chitosan and the hydrogel of dopamine and preparation method thereof Download PDF

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CN109180970A
CN109180970A CN201811005540.3A CN201811005540A CN109180970A CN 109180970 A CN109180970 A CN 109180970A CN 201811005540 A CN201811005540 A CN 201811005540A CN 109180970 A CN109180970 A CN 109180970A
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citric acid
dopamine
hydrogel
chitosan
preparation
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CN109180970B (en
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戴红莲
刘坤
李雪
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Wuhan University of Technology WUT
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Wuhan University of Technology WUT
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Abstract

The present invention relates to a kind of citric acid cross-linked chitosan and hydrogels of dopamine and preparation method thereof, the following steps are included: S1 is dissolved chitosan in acetic acid solution, at a certain temperature, dopamine is added and stirs to get blend solution, then citric acid is added, stirring is uniformly mixed it；Solution is placed under low temperature environment by S2, makes its fast cooling, and catalyst progress amidation cross-linking reaction is then added and obtains hydrogel；It is neutral that S3, which washs the gel after crosslinking to pH,.Beneficial effects of the present invention: 1, the present invention utilizes citric acid cross-linked chitosan and dopamine, the hydrogel of non-toxic degradable good using one kettle way biocompatibility；2, the hydrogel that the present invention is formed has ideal pore structure and mechanical property, provides good mentality of designing for the application of chitosan-based hydrogel.

Description

A kind of citric acid cross-linked chitosan and the hydrogel of dopamine and preparation method thereof
Technical field
The invention belongs to hydrogel preparation field, in particular to a kind of hydrogel of citric acid cross-linked chitosan and dopamine And preparation method thereof.
Background technique
Chitosan is unique a kind of alkaline polysaccharide in nature, has good biocompatibility, nontoxic, biodegradable, extensively The general wound tissue that is applied to repairs, skin repair and neural restoration, medicine controlled release carrier, and achieves well in these fields Effect can be prepared as hydrogel as bio-medical material as organizational project and hydrogel scaffold is provided.
Dopamine is a kind of neurotransmitter, monomer also known as 4- (2- ethylamino-) benzene -1,2- diphenol, while having catechol official It can roll into a ball and amino, dopamine can be improved the biocompatibility and cell adhesion of material, reduce inflammatory reaction, weaken blood Immune response, is widely used it as biomaterial.
Citric acid is a kind of ternary acid, has good regulating and controlling effect to cellular energy metabolism in vivo, is had anti- Oxidation and anti-inflammatory ability, while being also a kind of crosslinking agent of biological nontoxic, utilize the carboxyl and chitosan and DOPA of citric acid The amino of amine forms hydrogel using one kettle way, and the hydrogel of formation has ideal pore structure and mechanical property.
Hydrogel is a kind of hydrogel object that highly cross-linked hydrophilic polymeric not soluble in water has, and hydrogel has Gao Shuihan Amount, the porous structure of hydrogel is conducive to inside and outside tissue fluid and swaps, while can provide for cell adherence and growing into Bracket.Hydrogel is a type soft-tissue material, is commonly used for the material of skin injury reparation, spinal cord injury reparation, is had very big Function and effect and application prospect, aquagel is applied to spinal cord injury existing research at present, but not can solve spinal cord Secondary inflammatory problems after damage, and the introducing of citrate and dopamine can effectively mitigate secondary inflammation after spinal cord injury Reaction, provides good microenvironment for affected area, further promotes the reparation of spinal cord injury.
Summary of the invention
The present invention relates to a kind of citric acid cross-linked chitosan and hydrogel of dopamine and preparation method thereof, can be quick To a kind of good hydrogel of biocompatibility, with ideal pore structure and mechanical property, and there is anti-oxidant energy Power can inhibit to can reduce the inflammatory reaction of secondary damage after spinal cord injury while cicatrization for spinal cord injury.
The technical proposal adopted by the invention to solve the above technical problems is that: a kind of citric acid cross-linked chitosan and dopamine Hydrogel preparation method, which comprises the following steps:
S1 is dissolved chitosan in acetic acid solution, at a certain temperature, dopamine is added and stirs to get blend solution, so After be added citric acid, stirring is uniformly mixed it；
Solution is placed under low temperature environment by S2, makes its fast cooling, and catalyst is then added and carries out amidation cross-linking reaction Obtain hydrogel；
It is neutral that S3, which washs the gel after crosslinking to pH,.
According to the above scheme, temperature is 40~70 DEG C in step S1；Mixing time is 0.5~3 hour.
According to the above scheme, acetic acid solution volume fraction is 1%~2% in step S1, and chitosan additive amount is acetic acid solution 3wt%~4wt%.
According to the above scheme, citric acid in step S1, chitosan mass ratio be 1:6~12.
According to the above scheme, the molar ratio of citric acid and dopamine is 1:0~3 in step S1.
According to the above scheme, catalyst be added is 1- (3- dimethylamino-propyl) -3- ethyl carbodiimide/N- in step S2 One of n-hydroxysuccinimide (EDC/NHS), Geniposide and glutaraldehyde.
According to the above scheme, reaction temperature is 4 DEG C~25 DEG C in step S2.
According to the above scheme, it is water, ethyl alcohol or alkaline solution that agents useful for same is washed in step S3.
A kind of hydrogel of citric acid cross-linked chitosan and dopamine, it is characterised in that: apply any of the above-described preparation side Method is made.
Reaction mechanism of the present invention: this reaction prepares hydrogel using one kettle way, and reaction principle is citric acid as a kind of Crosslinking agent has amino group on chitosan and dopamine, amide occurs under the effect of the catalyst containing there are three carboxylic group Reaction, finally obtains hydrogel.
Beneficial effects of the present invention:
1, the present invention utilizes citric acid cross-linked chitosan and dopamine, good using one kettle way biocompatibility, nontoxic Degradable hydrogel；
2, the hydrogel that the present invention is formed has ideal pore structure and mechanical property, is the application of chitosan-based hydrogel Provide good mentality of designing.
Detailed description of the invention
Fig. 1 is the citric acid cross-linked chitosan of the embodiment of the present invention 1 and the infrared spectrogram of dopamine hydrogel；
Fig. 2 is the citric acid cross-linked chitosan of the embodiment of the present invention 1 and the ultraviolet spectrogram of dopamine hydrogel；
The citric acid cross-linked chitosan and the scanning electricity after the freeze-drying of dopamine hydrogel that Fig. 3 is the embodiment of the present invention 7 Mirror figure；
Fig. 4 is the citric acid cross-linked chitosan of the embodiment of the present invention 8 and the compression performance test chart of dopamine；
Fig. 5 is hydrogel of the invention to DPPH radicals scavenging lab diagram.
Specific embodiment
Below by specific implementation, invention is further explained, and however, the present invention is not limited to these examples.With Unless specific instructions, the reagent of use is the pure chemical reagent of commercially available chemistry to lower embodiment.
Embodiment 1
1.2g chitosan is dissolved in 1% acetic acid solution of 40ml and obtains the chitosan solution of 3wt%, under magnetic stirring Dissolution, is warming up to 40 DEG C, and 0.1806g dopamine is added and stirs 0.5h, is added 0.2g citric acid, in acquired solution, chitosan and The ratio of citric acid is 6/1, and the molar ratio of citric acid and dopamine is 1/1, completely and after mixing to its dissolution, rapidly Temperature is reduced to 4, DEG C addition EDC/NHS is poured into mold, is carried out catalysis amide cross-linking reaction and is obtained citric acid cross-linked chitosan It with the hydrogel of dopamine, is washed in NaOH solution, ethyl alcohol and deionized water three times respectively, obtains final hydrogel, pH For neutrality.
Infrared spectrogram as shown in Figure 1, in 1640cm-1Place and 1570cm-1The stretching vibration for corresponding to-CO-NH- is inhaled Peak is received, shows that amide reaction occurs after being added to citric acid, generates amide group, and the ultraviolet spectrogram of Fig. 2 is and independent Chitosan compare, there is apparent dopamine characteristic peak at 280nm in the hydrogel of synthesis, shows that dopamine is grafted to water On gel.
Embodiment 2
1.2g chitosan is dissolved in 1% acetic acid solution of 30ml and obtains the chitosan solution of 3wt%, under magnetic stirring Dissolution, is warming up to 40 DEG C, and 0.3612g dopamine is added and stirs 0.5h, is added 0.2g citric acid, in acquired solution, chitosan and The ratio of citric acid is 6/1, and the molar ratio of citric acid and dopamine is 1/2, completely and after mixing to its dissolution, rapidly Temperature is reduced to 4, DEG C addition EDC/NHS is poured into mold, is carried out catalysis amide cross-linking reaction and is obtained citric acid cross-linked chitosan It with the hydrogel of dopamine, is washed in NaOH solution, ethyl alcohol and deionized water three times respectively, obtains final pH as neutral water-setting Glue.
Embodiment 3
1.2g chitosan is dissolved in 1% acetic acid solution of 30ml and obtains the chitosan solution of 3wt%, under magnetic stirring Dissolution is warming up to 40 DEG C, and 0.5418g dopamine is added and stirs 0.5h, 0.2g citric acid, acquired solution chitosan and lemon is added The ratio of acid is 6/1, and the molar ratio of citric acid and dopamine is 1/3, completely and after mixing to its dissolution, is reduced rapidly DEG C EDC/NHS is added to 4 in temperature, pours into mold, carries out catalysis amide cross-linking reaction and obtains citric acid cross-linked chitosan and more The hydrogel of bar amine, is washed three times in NaOH solution, ethyl alcohol and deionized water respectively, obtains final pH as neutral hydrogel.
Embodiment 4
1.2g chitosan is dissolved in 2% acetic acid solution of 40ml and obtains the chitosan solution of 3wt%, under magnetic stirring Dissolution, is warming up to 70 DEG C, and 0.0903g dopamine is added and stirs 0.5h, is added 0.1g citric acid, in acquired solution, chitosan and The ratio of citric acid is 12/1, and the molar ratio of citric acid and dopamine is 1/1, completely and after mixing to its dissolution, Glutaraldehyde is added under room temperature, pours into mold, carries out catalytic crosslinking and reacts to obtain the water of citric acid cross-linked chitosan and dopamine Gel washs three times in NaOH solution, ethyl alcohol and deionized water respectively, obtains final pH as neutral hydrogel.
Embodiment 5
1.2g chitosan is dissolved in 1.5% acetic acid solution of 30ml and obtains the chitosan solution of 4wt%, in magnetic agitation Lower dissolution, is warming up to 60 DEG C, is added 0.2g citric acid, and in acquired solution, the ratio of chitosan and citric acid is 6/1, citric acid It is 1/0 with the molar ratio of dopamine, completely and after mixing to its dissolution, reduces rapidly temperature to 4, DEG C EDC/ is added NHS is poured into mold, is carried out catalysis amide cross-linking reaction and is obtained the hydrogel of citric acid cross-linked chitosan and dopamine, respectively It is washed in PBS solution, ethyl alcohol and deionized water three times, obtains final pH as neutral hydrogel.
Embodiment 6
1.2g chitosan is dissolved in 1% acetic acid solution of 40ml and obtains the chitosan solution of 3wt%, under magnetic stirring Dissolution, is warming up to 40 DEG C, and 0.5418g dopamine is added and stirs 0.5h, is added 0.2g citric acid, in acquired solution, chitosan and The ratio of citric acid is 6/1, and the molar ratio of citric acid and dopamine is 1/3, completely and after mixing to its dissolution, rapidly Temperature is reduced to 25 DEG C, Geniposide is added, pours into mold, catalysis amide cross-linking reaction is carried out and obtains citric acid cross-linked chitosan It with the hydrogel of dopamine, is washed in KOH solution, ethyl alcohol and deionized water three times respectively, obtains final pH as neutral water-setting Glue.
Embodiment 7
1.2g chitosan is dissolved in 2% acetic acid solution of 30ml and obtains the chitosan solution of 4wt%, under magnetic stirring Dissolution, is warming up to 70 DEG C, and 0.2709g dopamine is added and stirs 0.5h, is added 0.1g citric acid, in acquired solution, chitosan and The ratio of citric acid is 12/1, and the molar ratio of citric acid and dopamine is 1/3, completely and after mixing to its dissolution, fast Prompt drop low temperature is added EDC/NHS, pours into mold to 4 DEG C, and carrying out catalysis amide cross-linking reaction, to obtain citric acid crosslinking shell poly- The hydrogel of sugar and dopamine, is washed three times in KOH solution, ethyl alcohol and deionized water respectively, and obtaining final pH is neutral water Gel.
As shown in figure 3, gained hydrogel is freeze-dried, electron-microscope scanning is then shot, as can be seen from the figure water Gel has good pore structure.
Embodiment 8
1.2g chitosan is dissolved in 1% acetic acid solution of 30ml and obtains the chitosan solution of 4wt%, under magnetic stirring Dissolution, is warming up to 60 DEG C, and 0.2709g dopamine is added and stirs 0.5h, is added 0.15g citric acid, in acquired solution, chitosan and The ratio of citric acid is 6/1, and the molar ratio of citric acid and dopamine is 1/2, completely and after mixing to its dissolution, rapidly Temperature is reduced to 4, DEG C addition EDC/NHS is poured into mold, is carried out catalysis amide cross-linking reaction and is obtained citric acid cross-linked chitosan It with the hydrogel of dopamine, is washed in KOH solution, ethyl alcohol and deionized water three times respectively, obtains final pH as neutral water-setting Glue.
As shown in figure 4, be the compression performance test chart of hydrogel, it can as seen from the figure, hydrogel has good anti- Press performance.
As shown in figure 5, be removing lab diagram of the hydrogel containing different content dopamine to DPPH free radical, wherein CS Group is individual aquagel group, and CS-CA-DA1, CS-CA-DA2, CS-CA-DA3 is respectively 1,2 He of the embodiment of the present invention Hydrogel prepared by 3, it can be seen that with the addition of dopamine, the removing ratio of free radical is increased, this shows material Inoxidizability can increase.
The invention discloses citric acid cross-linked chitosan and dopamine hydrogel and preparation method thereof, this field the relevant technologies Personnel can use for reference present disclosure, and the appropriate links such as material and route that change are realized, material of the invention and method only introductory section Important experiment and part exemplary embodiments illustrate the contents of the present invention, but these examples are not intended to limit protection scope of the present invention.

Claims (9)

1. a kind of preparation method of the hydrogel of citric acid cross-linked chitosan and dopamine, which comprises the following steps:
S1 is dissolved chitosan in acetic acid solution, at a certain temperature, be added dopamine stir to get blend solution, then plus Enter citric acid, stirring is uniformly mixed it；
Solution is placed under low temperature environment by S2, makes its fast cooling, and catalyst progress amidation cross-linking reaction is then added and obtains Hydrogel；
It is neutral that S3, which washs the gel after crosslinking to pH,.
2. requiring the preparation method according to right 1, it is characterised in that: temperature is 40~70 DEG C in step S1；Mixing time It is 0.5~3 hour.
3. requiring the preparation method according to right 1, it is characterised in that: in step S1 acetic acid solution volume fraction be 1%~ 2%, chitosan additive amount is 3wt%~4wt% of acetic acid solution.
4. requiring the preparation method according to right 1, it is characterised in that: the mass ratio of citric acid, chitosan in step S1 For 1:6~12.
5. requiring the preparation method according to right 1, it is characterised in that: the molar ratio of citric acid and dopamine is in step S1 1:0~3.
6. requiring the preparation method according to right 1, it is characterised in that: catalyst be added is 1- (3- diformazan in step S2 One of aminopropyl) -3- ethyl carbodiimide/N-N- HOSu NHS (EDC/NHS), Geniposide and glutaraldehyde.
7. preparation method according to claim 1, it is characterised in that: reaction temperature is 4 DEG C~25 DEG C in step S2.
8. preparation method according to claim 1, it is characterised in that: in step S3 wash agents useful for same be water, ethyl alcohol or Alkaline solution.
9. a kind of hydrogel of citric acid cross-linked chitosan and dopamine, it is characterised in that: using any of claim 1~8 Item preparation method is made.
CN201811005540.3A 2018-08-30 2018-08-30 Citric acid crosslinked chitosan and dopamine hydrogel and preparation method thereof Active CN109180970B (en)

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CN113072716A (en) * 2021-03-17 2021-07-06 武汉理工大学 Preparation method of photo-crosslinked chitosan hydrogel
CN114209889A (en) * 2021-12-24 2022-03-22 中山大学附属第三医院（中山大学肝脏病医院） Modified chitosan/functional short peptide composite hydrogel and preparation method and application thereof
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CN115010958A (en) * 2022-05-13 2022-09-06 楼天女 Hydrogel for promoting wound healing and preparation method and application thereof
CN114805859A (en) * 2022-06-16 2022-07-29 安阳师范学院 Preparation method of heat-setting chitosan hydrogel
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CN115753933A (en) * 2022-12-22 2023-03-07 中国热带农业科学院南亚热带作物研究所 Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode
CN115753933B (en) * 2022-12-22 2023-08-11 中国热带农业科学院南亚热带作物研究所 Preparation method and application of carboxymethyl chitosan-based hydrogel modified electrode

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