CN110156915A - A kind of catechol/N- methacrylation chitosan derivatives and preparation method thereof - Google Patents
A kind of catechol/N- methacrylation chitosan derivatives and preparation method thereof Download PDFInfo
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- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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Abstract
A kind of catechol/N- methacrylation chitosan derivatives and preparation method thereof.Preparation method includes: that methacrylic anhydride is added drop-wise in chitosan solution by (1), in heating water bath sustained response a few hours, chitosan can be completed and be acylated, adjust reaction mixture pH value to 5.0；(2) by 3; 4- 4-dihydroxy benzaldehyde is dissolved in the in the mixed solvent of methanol and water; it is added drop-wise in the reaction mixture of above-mentioned steps (1) acquisition again; then the sustained response a few hours under nitrogen protection, heating water bath and stirring condition are added sodium borohydride and carry out reduction generation schiff bases；(3) pH value of above-mentioned reaction mixture is adjusted to 7.0 using sodium hydroxide solution; and it is transferred in dialysis tubing; it dialyses 3 days in nitrogen protection, heating water bath and deionized water environment, finally freeze-drying is final to obtain catechol/methacrylation chitosan.The characteristics of wherein carbon-carbon double bond and catechol group assign chitosan photocurable and tissue adherence respectively.
Description
Technical field
The present invention relates to a kind of photocurable, injectable and the chitosan derivatives and its system with strength tissue adherence
Preparation Method belongs to bioabsorbable polymer material preparation and modified field.
Background technique
Chitosan is the alkalescent natural polysaccharide that amino is uniquely had in nature, due to good biocompatibility, life
Biodegradable makes it can be applied to the fields such as drug release, organizational project and wound dressing.The chitosan water-setting studied at present
Glue is concentrated mainly on temperature sensitive aquagel and Geniposide or more hydroformylation cross-linked chitosan hydrogels.However above-mentioned water-setting
Glue there are apparent crosslinking time too long (10 minutes to 60 minutes), need to add a large amount of second components influence degradabilities,
A series of problems, such as crosslinking agent is more toxic.Thus utilize reaction active groups (amino and hydroxyl) rich in chitosan
Acylation reaction or esterification assign the photo curable performance of chitosan, this will widen the injectable chitosan based on photocuring
Hydrogel is in organizational project, drug release (package or load bioactive substance, such as drug, protein and growth factor) and wound
The application range of the fields of biomedicine such as wound reparation.Furthermore there is also cellular affinity and tissue adherences for aquagel
The problems such as poor, restricts it in the application of the fields of biomedicine such as organizational project, drug release and wound repair.
Summary of the invention
Present invention aims at can not be that there is photocurable strength to organize to glue again for existing chitosan derivatives presence
The disadvantages of attached property, proposes that two-step method synthesizes photocurable, injectable and the chitosan derivatives with strength tissue adherence:
Catechol/N- methacrylation chitosan.
A kind of catechol/N- methacrylation chitosan derivatives are a kind of photocurable, injectable and have strength
The chitosan material of tissue adherence, it is characterised in that: catechol/N- methacrylation chitosan has following structure formula:
One kind being based on catechol as described above/N- methacrylation chitosan preparation method, which is characterized in that packet
Containing following steps:
(1) methacrylic anhydride is slowly dropped in chitosan acetic acid solution, in heating water bath and the condition of stirring
It lower sustained response a few hours, can be completed that chitosan is acylated, adjust the pH value of reaction mixture to 5.0；
(2) 3,4- 4-dihydroxy benzaldehyde is dissolved in the in the mixed solvent of methanol and water, then is slowly dropped to above-mentioned steps
(1) in the reaction mixture obtained, and the sustained response a few hours under nitrogen protection, heating water bath and stirring condition, so
Sodium borohydride is added afterwards and carries out reduction generation schiff bases；
(3) pH value of above-mentioned reaction mixture is adjusted to 7.0 using sodium hydroxide solution, and is transferred in dialysis tubing,
It dialyses 3 days in nitrogen protection, heating water bath and deionized water environment, finally freeze-drying is final to obtain catechol/methyl
Acrylated chitosan.
Further, the mass concentration of chitosan described in step (1) is 0.45~3.15%；Methacrylic anhydride with
Chitosan mass ratio is 0.25~0.78；Bath temperature is 40~80 DEG C；Reaction time is 6~18 hours.
Further, 3,4- 4-dihydroxy benzaldehyde described in step (2) and chitosan mass ratio are 0.75~3.85；Water
Bath temperature is 50~70 DEG C；Reaction time is 2~4 hours；The quality of required solid sodium borohydride is 0.2~1.5g.
Further, the mass concentration of the sodium hydrate aqueous solution is 0.1~1.2%, and bath temperature is 35~50
℃。
The present invention for chitosan derivatives at this stage exist can not can photocuring there is strength tissue adherence again
The disadvantages of, prepare photocurable, injectable and the chitosan derivatives with strength tissue adherence for the first time by two-step method:
Catechol/N- methacrylation chitosan.And preparation method is simple and easy, the catechu for the chitosan derivatives prepared
Phenol functional group degree of substitution can be regulated and controled by 3,4- 4-dihydroxy benzaldehyde with chitosan molar ratio, be conducive to prepare a system
Arrange the chitosan derivatives of different catechol degree of substitution.
Detailed description of the invention
Fig. 1 catechol/N- methacrylation chitosan1H NMR spectra；
Fig. 2 catechol/N- methacrylation chitosan ultraviolet-visible spectrogram；
Fig. 3 catechol/N- methacrylation chitosan solution is coated on pig skin surfaces (left side), by light cross-linking radiation
Afterwards, certain weight (right side) can be born after being bonded to each other；
Fig. 4 is that catechol/N- methacrylation chitosan has following structure formula.
Specific embodiment
Embodiment 1
The chitosan of 1g is dissolved in the acetic acid aqueous solution that concentration of volume percent is 1%, is configured to mass percent
The chitosan solution that concentration is 1%.The methacrylic anhydride of 0.25g is added to above-mentioned chitosan in a manner of being slowly added dropwise
In solution, 6h is sufficiently reacted in the environment of 40 DEG C of stirring in water bath, and adjusts mixed solution pH to 5.0 after reaction.Then will
3, the 4- 4-dihydroxy benzaldehyde of 0.75g is dissolved in the methanol of 10mL and the mixed solvent (volume ratio 1:1) of water, by 3,4- bis-
Hydroxy benzaldehyde solution is added in above-mentioned chitosan reaction mixed solution in a manner of being slowly added dropwise, and nitrogen protection,
Sustained response 2 hours under conditions of 50 DEG C of stirring in water bath.The solid sodium borohydride of 0.2g is added to above-mentioned reaction solution to carry out
Reduction reaction.It uses mass concentration to adjust reaction mixture pH to 7.0 for 0.5% sodium hydroxide solution, and is transferred to
It analyses in pipe (molecular cut off be 8000~14000), dialyses 3 in nitrogen protection, 35 DEG C of stirring in water bath, deionized water environment
It, the solution after dialysis obtains catechol/methacrylation chitosan by freeze-drying is final.
Using nuclear magnetic resonance spectroscopy (1H-NMR catechol/methacrylation chitosan hydrogen chemical shifts) are characterized,
Its spectrogram is as shown in Figure 1.It is signal peak occur at 5.4 and 5.7ppm in chemical shift, belongs to vinyl (=CH2) proton peak；
Furthermore there is signal peak at 6.6~6.8ppm of chemical shift, be the phenyl ring proton peak of catechol group.This shows chemical modification
Carbon-carbon double bond and catechol group are introduced in chitosan molecule chain afterwards.Further use ultraviolet-visible spectrum analysis, such as Fig. 2
It is shown, there is the absorption peak of typical catechol group in 280nm.During catechol/methacrylation chitosan is dissolved in
Property aqueous solution in (containing mass concentration be 0.1% photoinitiator LAP and methylene blue dye), and be coated on pigskin tissue
Two panels pigskin is then pressed 5 minutes by blue light crosslinking (wavelength is 400~500nm), it is found that its adhesion strength can by surface
The object of constant weight is born, as shown in Figure 3.
Embodiment 2
The chitosan of 1g is dissolved in the acetic acid aqueous solution that concentration of volume percent is 1%, is configured to mass percent
The chitosan solution that concentration is 1%.The methacrylic anhydride of 0.5g is added to above-mentioned chitosan in a manner of being slowly added dropwise
In solution, 6h is sufficiently reacted in the environment of 40 DEG C of stirring in water bath, and adjusts mixed solution pH to 5.0 after reaction.Then will
3, the 4- 4-dihydroxy benzaldehyde of 0.75g is dissolved in the methanol of 10mL and the mixed solvent (volume ratio 1:1) of water, by 3,4- bis-
Hydroxy benzaldehyde solution is added in above-mentioned chitosan reaction mixed solution in a manner of being slowly added dropwise, and nitrogen protection,
Sustained response 2 hours under conditions of 50 DEG C of stirring in water bath.The solid sodium borohydride of 0.2g is added to above-mentioned reaction solution to carry out
Reduction reaction.It uses mass concentration to adjust reaction mixture pH to 7.0 for 0.5% sodium hydroxide solution, and is transferred to
It analyses in pipe (molecular cut off be 8000~14000), dialyses 3 in nitrogen protection, 35 DEG C of stirring in water bath, deionized water environment
It, the solution after dialysis obtains catechol/methacrylation chitosan by freeze-drying is final.
Embodiment 3
The chitosan of 1g is dissolved in the acetic acid aqueous solution that concentration of volume percent is 1%, is configured to mass percent
The chitosan solution that concentration is 1%.The methacrylic anhydride of 0.25g is added to above-mentioned chitosan in a manner of being slowly added dropwise
In solution, 6h is sufficiently reacted in the environment of 40 DEG C of stirring in water bath, and adjusts mixed solution pH to 5.0 after reaction.Then will
3, the 4- 4-dihydroxy benzaldehyde of 1g is dissolved in the methanol of 10mL and the mixed solvent (volume ratio 1:1) of water, by 3,4- dihydroxy
Benzaldehyde solution is added in above-mentioned chitosan reaction mixed solution in a manner of being slowly added dropwise, and in nitrogen protection, 50
Sustained response 2 hours under conditions of DEG C stirring in water bath.The solid sodium borohydride of 0.2g is added to above-mentioned reaction solution to be gone back
Original reaction.It uses mass concentration to adjust reaction mixture pH to 7.0 for 0.5% sodium hydroxide solution, and is transferred to dialysis
In pipe (molecular cut off is 8000~14000), dialyse 3 days in nitrogen protection, 35 DEG C of stirring in water bath, deionized water environment,
Solution after dialysis obtains catechol/methacrylation chitosan by freeze-drying is final.
Embodiment 4
The chitosan of 1g is dissolved in the acetic acid aqueous solution that concentration of volume percent is 1%, is configured to mass percent
The chitosan solution that concentration is 1%.The methacrylic anhydride of 0.5g is added to above-mentioned chitosan in a manner of being slowly added dropwise
In solution, 6h is sufficiently reacted in the environment of 40 DEG C of stirring in water bath, and adjusts mixed solution pH to 5.0 after reaction.Then will
3, the 4- 4-dihydroxy benzaldehyde of 1g is dissolved in the methanol of 10mL and the mixed solvent (volume ratio 1:1) of water, by 3,4- dihydroxy
Benzaldehyde solution is added in above-mentioned chitosan reaction mixed solution in a manner of being slowly added dropwise, and in nitrogen protection, 50
Sustained response 2 hours under conditions of DEG C stirring in water bath.The solid sodium borohydride of 0.2g is added to above-mentioned reaction solution to be gone back
Original reaction.It uses mass concentration to adjust reaction mixture pH to 7.0 for 0.5% sodium hydroxide solution, and is transferred to dialysis
In pipe (molecular cut off is 8000~14000), dialyse 3 days in nitrogen protection, 35 DEG C of stirring in water bath, deionized water environment,
Solution after dialysis obtains catechol/methacrylation chitosan by freeze-drying is final.
Claims (5)
1. a kind of catechol/N- methacrylation chitosan derivatives, it is characterised in that: catechol/N- methacrylation
Chitosan has following structure formula:
2. a kind of based on catechol described in right 1/N- methacrylation chitosan derivatives preparation method, feature exists
In comprising the steps of: (1) methacrylic anhydride is slowly dropped in chitosan acetic acid solution, in heating water bath and is stirred
It sustained response a few hours under conditions of mixing, can be completed that chitosan is acylated, adjust the pH value of reaction mixture to 5.0；(2) will
3,4- 4-dihydroxy benzaldehydes are dissolved in the in the mixed solvent of methanol and water, then are slowly dropped to the reaction of above-mentioned steps (1) acquisition
In mixed solution, and the sustained response a few hours under nitrogen protection, heating water bath and stirring condition, sodium borohydride is then added
It carries out reduction and generates schiff bases；(3) pH value of above-mentioned reaction mixture is adjusted to 7.0 using sodium hydroxide solution, and shifted
It to dialysis tubing, dialyses 3 days in nitrogen protection, heating water bath and deionized water environment, finally freeze-drying is final to be obtained
Catechol/methacrylation chitosan.
3. the catechol according to right 2/N- methacrylation chitosan derivatives preparation method, it is characterised in that step
Suddenly the mass concentration of chitosan described in (1) is 0.45~3.15%；Methacrylic anhydride and chitosan mass ratio are 0.25
~0.78；Bath temperature is 40~80 DEG C；Reaction time is 6~18 hours.
4. the catechol according to right 2/N- methacrylation chitosan derivatives preparation method, it is characterised in that step
Suddenly 3,4- 4-dihydroxy benzaldehyde described in (2) and chitosan mass ratio are 0.75~3.85；Bath temperature is 50~70 DEG C；Instead
It is 2~4 hours between seasonable；The quality of required solid sodium borohydride is 0.2~1.5g.
5. the catechol according to right 2/N- methacrylation chitosan derivatives preparation method, it is characterised in that step
Suddenly the mass concentration of sodium hydrate aqueous solution described in (3) is 0.1~1.2%, and bath temperature is 35~50 DEG C.
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Cited By (4)
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| CN113332487A (en) * | 2021-05-26 | 2021-09-03 | 江苏诺瓦立医疗用品有限公司 | Biological tissue adhesive |
| CN115232574A (en) * | 2022-07-28 | 2022-10-25 | 南京林业大学 | Functionalized mica-reinforced anticorrosive flame-retardant soybean protein adhesive and preparation method thereof |
| CN115337464A (en) * | 2022-08-15 | 2022-11-15 | 成都斐洛智凝生物科技有限公司 | Preparation method of modified bacterial cellulose membrane for periodontal tissue repair |
| CN117379587A (en) * | 2023-09-15 | 2024-01-12 | 中山大学中山眼科中心 | Tissue adhesive material, and preparation method and application thereof |
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| CN115337464B (en) * | 2022-08-15 | 2023-12-15 | 成都斐洛智凝生物科技有限公司 | Preparation method of modified bacterial cellulose membrane for periodontal tissue repair |
| CN117379587A (en) * | 2023-09-15 | 2024-01-12 | 中山大学中山眼科中心 | Tissue adhesive material, and preparation method and application thereof |
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