CN108484936A - A kind of hydrogel and its preparation method and application prepared by graft modification material - Google Patents
A kind of hydrogel and its preparation method and application prepared by graft modification material Download PDFInfo
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- CN108484936A CN108484936A CN201810272839.9A CN201810272839A CN108484936A CN 108484936 A CN108484936 A CN 108484936A CN 201810272839 A CN201810272839 A CN 201810272839A CN 108484936 A CN108484936 A CN 108484936A
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- hydrogel
- polylysine
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- 239000000017 hydrogel Substances 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000463 material Substances 0.000 title claims abstract description 18
- 238000012986 modification Methods 0.000 title claims abstract description 12
- 230000004048 modification Effects 0.000 title claims abstract description 12
- 229920000656 polylysine Polymers 0.000 claims abstract description 49
- 108010039918 Polylysine Proteins 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000010521 absorption reaction Methods 0.000 claims abstract description 15
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 13
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 16
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 10
- 206010052428 Wound Diseases 0.000 claims description 8
- 208000027418 Wounds and injury Diseases 0.000 claims description 8
- 238000000502 dialysis Methods 0.000 claims description 5
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical class C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000178 monomer Substances 0.000 claims description 4
- -1 Amber acid imide Chemical class 0.000 claims description 3
- 208000002847 Surgical Wound Diseases 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 230000001684 chronic effect Effects 0.000 claims description 3
- 206010012601 diabetes mellitus Diseases 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 2
- 230000008439 repair process Effects 0.000 claims description 2
- 229920002892 amber Polymers 0.000 claims 1
- 229920002401 polyacrylamide Polymers 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 5
- 230000003115 biocidal effect Effects 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 230000037314 wound repair Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 8
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 229920000642 polymer Polymers 0.000 description 7
- 239000003643 water by type Substances 0.000 description 7
- 108010010803 Gelatin Proteins 0.000 description 6
- 239000008273 gelatin Substances 0.000 description 6
- 229920000159 gelatin Polymers 0.000 description 6
- 235000019322 gelatine Nutrition 0.000 description 6
- 235000011852 gelatine desserts Nutrition 0.000 description 6
- 239000003292 glue Substances 0.000 description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 239000005357 flat glass Substances 0.000 description 5
- 210000001519 tissue Anatomy 0.000 description 5
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 4
- 230000000845 anti-microbial effect Effects 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 239000000499 gel Substances 0.000 description 4
- 230000005764 inhibitory process Effects 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 229910021538 borax Inorganic materials 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 description 3
- 229920001817 Agar Polymers 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 241000588724 Escherichia coli Species 0.000 description 2
- 108010037362 Extracellular Matrix Proteins Proteins 0.000 description 2
- 102000010834 Extracellular Matrix Proteins Human genes 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- 241000191967 Staphylococcus aureus Species 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 239000008272 agar Substances 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 229920006317 cationic polymer Polymers 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 210000002744 extracellular matrix Anatomy 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 2
- 239000012567 medical material Substances 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229920005615 natural polymer Polymers 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 241000186046 Actinomyces Species 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 235000008331 Pinus X rigitaeda Nutrition 0.000 description 1
- 235000011613 Pinus brutia Nutrition 0.000 description 1
- 241000018646 Pinus brutia Species 0.000 description 1
- 208000031737 Tissue Adhesions Diseases 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000003926 acrylamides Chemical class 0.000 description 1
- 125000003647 acryloyl group Chemical group O=C([*])C([H])=C([H])[H] 0.000 description 1
- 125000003275 alpha amino acid group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003797 essential amino acid Substances 0.000 description 1
- 235000020776 essential amino acid Nutrition 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000001963 growth medium Substances 0.000 description 1
- 230000035876 healing Effects 0.000 description 1
- 230000023597 hemostasis Effects 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 235000015097 nutrients Nutrition 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
- 230000029663 wound healing Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0009—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials
- A61L26/0019—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form containing macromolecular materials obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L26/00—Chemical aspects of, or use of materials for, wound dressings or bandages in liquid, gel or powder form
- A61L26/0061—Use of materials characterised by their function or physical properties
- A61L26/008—Hydrogels or hydrocolloids
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/04—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polycarbonamides, polyesteramides or polyimides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
- C08J2377/04—Polyamides derived from alpha-amino carboxylic acids
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Health & Medical Sciences (AREA)
- Veterinary Medicine (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Engineering & Computer Science (AREA)
- Public Health (AREA)
- Materials Engineering (AREA)
- Dispersion Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Preparation (AREA)
- Materials For Medical Uses (AREA)
Abstract
The present invention relates to the hydrogels and its preparation method and application prepared by a kind of graft modification material.The hydrogel is the formation of polylysine grafted polyacrylamide with inierpeneirating network structure hydrogel.Hydrogel provided by the invention not only has stronger mechanical property, and suitable wound adhesiveness, excellent antibiotic property, also has higher saturated water absorption, can be used for preparing wound repair product.The preparation method of the hydrogel provided by the invention is simple for process, yield is high.
Description
Technical field
The invention belongs to medical material technical fields, more particularly, to the water-setting prepared by a kind of graft modification material
Glue and its preparation method and application.
Background technology
Hydrogel medical trauma auxiliary material is a kind of novel wound dressings developed in recent years.With traditional auxiliary material phase
Than hydrogel can promote wound preferably to heal, mitigate the pain of patient, it can improve the microenvironment of the surface of a wound, inhibit bacterium
Growth.
Japanese scholars in 1977 cultivate from actinomyces extracted in filtered fluid it is a kind of containing 25~30 lysine residues
Homotype monomer-polymer.This lysine polymers be lysine residue lead to the amide key connection that α-carboxyl and epsilon-amino are formed and
At, therefore claim epsilon-polylysine.Epsilon-polylysine is applied to prepare hydrogel as natural polymer, and advantage is following side
Face：First, a large amount of amino active group is possessed on strand, under aqueous solution or acidic environment on binding hydrogen ions band
Positive charge forms cationic polymer, and this cationic polymer can be very good to be incorporated in cell surface to reach wound group
The purpose of bonding is knitted, secondly as polylysine is natural macromolecular material, there is good biocompatibility, and it is dropped
Solution product lysine is essential amino acid, and finally, polylysine is amino acid polymer, water-soluble good, is overcome
Numerous organization healing materials are insoluble in the difficulty of water.But hydrogel, main method are prepared using polylysine in the prior art
It is cross-linking radiation, chemical crosslinking, or prepares hydrogel by way of physical mixed.Hydrogel prepared by these technologies exists
The problem of with poor mechanical property, cause hydrogel frangible and reduce its adhesiveness, limits its clinical application.
Therefore, developing a kind of polylysine hydrogel that mechanical property is good has important research significance and application value.
Invention content
It is an object of the invention to overcome lacking for polylysine hydrogel medical material poor mechanical property in the prior art
Point and insufficient, provides that a kind of mechanical property is relatively strong and the hydrogel with suitable tissue adherence.Water-setting provided by the invention
Glue is the hydrogel with inierpeneirating network structure that grafted polyacrylamide obtains on polylysine, by natural polymer and synthesis
High molecular advantage combines, and can retain the high molecular mechanical strength of synthesis and possess good biocompatibility, fit
The tissue adherence of conjunction, excellent anti-microbial property, while improving the saturated water absorption of colloid.
Another object of the present invention is to provide the preparation methods of above-mentioned hydrogel.
Another object of the present invention is to provide above-mentioned hydrogels to prepare chronic wound reparation closure product, diabetes
Repair the application in product or surgical wound surface reparation product.
For achieving the above object, the present invention adopts the following technical scheme that：
A kind of hydrogel prepared by graft modification material, the hydrogel are the tool that polylysine grafted polyacrylamide is formed
There is inierpeneirating network structure hydrogel.
The present invention provides a kind of water-settings with preferable mechanical property for polylysine obtain after graft modification
Glue, which forms interpenetrating cross-linked network by the grafted polyacrylamide on polylysine, to substantially increase it
Mechanical property, and there is good tissue adherence, while the saturated water absorption of colloid is improved, anti-microbial property is excellent.
Preferably, the grafting rate of the polylysine is 10%~45%.
Preferably, the molecular weight of the polylysine is 3000~5000Da.The molecular weight of polylysine is arrived 3000
Between 5000 dalton, in natural extracellular matrix (ECM) protein ingredient and function it is similar.
Preferably, the tensile elongation of the hydrogel be 1000%~2500%, saturated water absorption be 400%~
800%.
Preferably, the tissue adhesion intensity of the hydrogel is 1~3Mpa, the water-setting prepared better than simple polylysine
Glue.
The present invention also provides the preparation method of above-mentioned hydrogel, the preparation method includes the following steps：
S1：1- (3- dimethylamino-propyls) -3- ethyl carbodiimide EDC and N- hydroxysuccinimidyls are added into polylysine aqueous solution
Acid imide NHS dialyses after reacting 4~8h, and solution is lyophilized up to modified polylysine after taking dialysis；
S2：Addition acrylamide monomer is stirred after modified polylysine obtained by S1 is dissolved in water, and light is added after mixing
Initiator ammonium persulfate and N, N '-methylene-bisacrylamides continue ultraviolet light after stirring；
S3：Then it is 8~10 to adjust pH, is stood to get the hydrogel.
The preparation method of hydrogel provided by the invention, can be obtained it is above-mentioned have that mechanical property is strong, saturated water absorption is high and
Hydrogel with preferable wound healing effect.It is activated to obtain by the carboxyl to polylysine first modified poly-
Lysine, then by photopolymerization reaction obtain include polyacrylamide and modified polylysine mixture, finally by poly- third
Amino is grafted to formation interpenetrating cross-linked network structure on the carboxyl of polylysine in acrylamide, to greatly improve its mechanical strength
And saturated water absorption, there is good antibiotic property.The preparation method of the hydrogel material provided by the invention, simple for process, yield
It is high.
Polylysine can be dissolved in deionized water, purified water, ultra-pure water etc., it is preferable that polylysin solution in the present invention
Mass concentration be 5%~10%.
Preferably, the mass ratio of EDC described in S1 and NHS is 1:The quality sum of 1~5, the EDC and NHS rely with poly-
The mass ratio of propylhomoserin is 5:100~10:100；Preferably, the mass ratio of the EDC and NHS is 1:1.Gathering with this condition relies
Activated carboxylic situation on propylhomoserin is best, is conducive to improve grafting rate, obtains the stronger hydrogel of mechanical property.
Preferably, it is 10~20% that modified polylysine described in S2, which is dissolved in the mass concentration after water,；The modification is poly- to be relied
The mass ratio of propylhomoserin and acrylamide monomer is 1:10~10:1, preferably 1:1.The present inventor is by repeatedly studying hair
Existing, its grafting rate can be influenced by controlling the mass ratio of modified polylysine and acrylamide monomer, and in a certain range, grafting rate is got over
The mechanics ability of height, gained interpenetration network hydrogel is stronger.And the increase of modified polylysine dosage used, hydrogel are satisfied
It gradually increases with water absorption rate, is continuously decreased again with the increase of modified polylysine dosage after reaching maximum value.Due to water-setting
- COO on the strand of glue both containing partial ionizationWith-NH3 +, contain unionized-COOH and-NH simultaneously2.On the one hand by
In-COOWith-NH3 +Presence so that the hydrophily of hydrogel is increased, be more prone to inside water diffusion to gel, make gel
Water absorbing properties increase；On the other hand due to-COOWith-NH3 +Easily formed inner salt, along with there are unionized-COOH and-
NH2, gel molecular interchain easily forms hydrogen bond, both plays the role of physical crosslinking point；When the crosslink density of gel increases, inhale
It is aqueous to decline.
Preferably, the mass ratio of ammonium persulfate and N in S2, N '-methylene-bisacrylamides are 1:1；Ammonium persulfate with
The quality sum of N, N '-methylene-bisacrylamide and the mass ratio of acrylamide monomer are 1:100~5:100.
Preferably, photoinitiator ammonium persulfate and N, N '-methylene-bisacrylamide are added in S2, continues mixing time
For 30min~2h.
Preferably, the wavelength of ultraviolet light is 300~500nm in S2.It is further preferable that the wavelength of ultraviolet light is 350 in S2
~370nm, ultraviolet light time are 8~12h.
Preferably, pH is adjusted to 9 in S3.This condition is modified the degree of ionization highest of activated carboxyl on polylysine.
Preferably, time of repose is 30min in S3.
Above-mentioned hydrogel is preparing chronic wound reparation closure product, diabetes reparation product or surgical wound surface reparation production
Application in product is also within the scope of the present invention.
Compared with prior art, the present invention has the advantages that：
Hydrogel prepared by graft modification material provided by the invention is the tool that grafted polyacrylamide obtains on polylysine
There is polylysine-Polyacrylamide Grafted gelatinous polymer of interpenetrating cross-linked network, not only there is stronger mechanical property, again
Good biocompatibility, suitable tissue adherence, excellent anti-microbial property can be possessed, while improving the saturation water suction of colloid
Rate can be used for preparing wound repair product.The preparation method of the material provided by the invention, it is simple for process, yield is high.
Description of the drawings
Fig. 1 is inhibition zone.
Specific implementation mode
With reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And it replaces and belongs to scope of the present invention.
Embodiment 1
The present embodiment provides hydrogels, and the hydrogel by obtaining following preparation method：
5g polylysines (molecular weight is 3000~5000) are weighed in container, 100ml deionized waters are added, are stirred to dissolve,
0.125g EDC and 0.125g NHS are added, react 4h.Solution is taken out, dialysis takes solution in bag filter to be lyophilized, obtains modification
Polylysine.It weighs 2g and is modified polylysine in container, 10ml deionized waters are added, stir to dissolve, 2g propylene is added
Amide monomer stirs to dissolve in container.0.01g ammonium persulfate photoinitiators, the N of 0.01g, N '-di-2-ethylhexylphosphine oxides is added
Acrylamide continues to stir 30min in container.Solution is poured into vessel, is irradiated using 365nm ultraviolet light generators
Night.Use sodium borate buffer solution tune pH to 8.30min is stood, polylysine-polyacrylamide that grafting rate is 10% is obtained
It is grafted gelatinous polymer.
Embodiment 2
The present embodiment provides a kind of hydrogels, and the hydrogel by obtaining following preparation method：
1.5g polylysines (molecular weight is 3000~5000) are weighed in container, 60ml purified waters are added, is stirred to dissolve, adds
Enter 0.25g EDC and 1.25g NHS, reacts 8h.Solution is taken out, dialysis takes solution in bag filter to be lyophilized, and obtains modified gathering and relies
Propylhomoserin.It weighs 2g and is modified polylysine in container, 20ml deionized waters are added, stir to dissolve, 10g acryloyls are added
Amine monomers stir to dissolve in container.0.05g ammonium persulfate photoinitiators, the N of 0.05g, N '-di-2-ethylhexylphosphine oxides third is added
Acrylamide continues to stir 1h in container.Solution is poured into vessel, is irradiated overnight using 350nm ultraviolet light generators.It uses
Sodium borate buffer solution tune pH to 10.30min is stood, it is solidifying to obtain polylysine-Polyacrylamide Grafted that grafting rate is 45%
Gum polymers.
Embodiment 3
The present embodiment provides a kind of hydrogels, and the hydrogel by obtaining following preparation method：
5g polylysines (molecular weight is 3000~5000) are weighed in container, 50ml ultra-pure waters are added, make it dissolve, are added
0.25g EDC and 0.5g NHS react 6h.Solution is taken out, dialysis takes solution in bag filter to be lyophilized, and obtains modified poly- bad ammonia
Acid.It weighs 2g and is modified polylysine in container, 15ml deionized waters are added, stir to dissolve, 0.5g acrylamides are added
Monomer stirs to dissolve in container.0.025g ammonium persulfate photoinitiators, the N of 0.025g, N '-di-2-ethylhexylphosphine oxides third is added
Acrylamide continues to stir 2h in container.Solution is poured into vessel, is irradiated overnight using 370nm ultraviolet light generators.It uses
Sodium borate buffer solution tune pH to 9.30min is stood, it is solidifying to obtain polylysine-Polyacrylamide Grafted that grafting rate is 32%
Gum polymers.
Comparative example 1
This comparative example provides a kind of polylysine hydrogel, and the material by obtaining following preparation method：
5g polylysines (molecular weight is 3000~5000) are weighed in container, 50ml ultra-pure waters are added, make it dissolve, are added
0.25g EDC and 0.25g NHS react 16h.Co60 gamma-rays 40kGy irradiates 12h, obtains polylysine hydrogel.
Performance test
(1) Mechanics Performance Testing
The sample of Example 1~3 and comparative example 1, the size for making hydrogel column sample are 1cm × 2cm, abundant stress pine
Extension test is carried out after relaxation, test speed is set as 100mm/min, calculates tensile elongation.
Tensile elongation=(L1-L0)/L0* 100%, wherein L0For initial length, L1For length after stretching.
1 tensile elongation test result of table
| Test case | L0/cm | L1/cm | Tensile elongation |
| Embodiment 1 | 2 | 24 | 1100% |
| Embodiment 2 | 2 | 48 | 2300% |
| Embodiment 3 | 2 | 32 | 1500% |
| Comparative example 1 | 2 | 6 | 200% |
According to the result of table 1 it is found that the power of polylysine-polyacrylamide hydrogel of the graft modification material preparation of the present invention
Learn the mechanical property that performance is apparently higher than common polylysine hydrogel.
(2) antibacterial experiment
Bacterium can draw the nutrient in culture medium and mushroom out in the medium, once it is put into the medium
When material with antibacterial functions, the biocidal property of material causes the bacterium of surrounding materials to be difficult to survive, this is resulted in
It will appear obvious sterile circle, also known as inhibition zone around sample, as shown in Figure 1.
Staphylococcus aureus and Escherichia coli are chosen as test strain, table is tested using agar plate diffusion method
Levy the antibacterial effect of hydrogel.Cylindrical hydrogel is placed in the agar medium center for being coated with bacterium solution, in 37 DEG C of perseverances
It is cultivated 24 hours in warm incubator, measures the diameter of inhibition zone.The antibiotic property of hydrogel is indicated with antibacterial bandwidth (H).Wherein
The calculating of antibacterial bandwidth (H) is as shown in Equation 1：
(formula 1)
Wherein：D is the average value (mm) of inhibition zone outer diameter；D is the diameter (mm) of hydrogel.
Sample in selection example 1 carries out above-mentioned antibacterial experiment test, to Escherichia coli and staphylococcus aureus
Maximum antibacterial bandwidth is respectively (9.56 ± 0.13) mm and (12.35 ± 0.72) mm, and anti-microbial property is excellent.
(3) bonding experiment
In order to measure adhesiveness, come simulated human tissue, the present invention is measured using in one layer of gelatin of heavy sheet glass on piece even spread
Adhesion strength of the middle hydrogel to gelatin.Aqueous gelatin solution is uniformly coated on 5mmx20mmx50mm sheet glass.It is placed in 70 DEG C
In baking oven required gelatin sheet glass is obtained after residual moisture in 30min removings gelatin.Then two pieces of gelatin sheet glass phase interconnections
It connects, is clamped after one layer of hydrogel of overlapping even spread, after placing 30min, surveyed at room temperature using omnipotent mechanics machine
Try the adhesive strength of two blocks of sheet glass, chuck speed 5mm/min.
Hydrogel made from Example 1~3 and comparative example 1 is tested according to the method described above respectively.As a result as follows：
2 adhesion test result of table
| Experimental example | Adhesive strength |
| Embodiment 1 | 1.53MPa |
| Embodiment 2 | 2.24MPa |
| Embodiment 3 | 1.74MPa |
| Comparative example 1 | 0.32MPa |
(4) saturated water absorption is tested
Take sample, quality m0, it is soaked in PBS solution, is impregnated for 24 hours at 37 DEG C.Glue is taken out, is weighed, glue after being impregnated
The quality of body is m1, calculate saturated water absorption=(m1-m0)/m0* 100%
3 saturated water absorption experimental result of table
| Sample | m0 | m1 | Saturated water absorption |
| Embodiment 1 | 1g | 4.6g | 360% |
| Embodiment 2 | 1g | 7.8g | 680% |
| Embodiment 3 | 1g | 5.2g | 420% |
| Comparative example 1 | 1g | 2.4g | 140% |
The hydrogel that various embodiments of the present invention provide has higher saturated water absorption, and improving colloid saturated water absorption can be abundant
The absorption surface of a wound oozes night and increases physics hemostasis by compression effect.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from the spirit and principles of the present invention made by changes, modifications, substitutions, combinations, simplifications,
Equivalent substitute mode is should be, is included within the scope of the present invention.
Claims (10)
1. the hydrogel prepared by a kind of graft modification material, which is characterized in that the hydrogel is that polylysine is grafted poly- third
The hydrogel with inierpeneirating network structure that acrylamide is formed.
2. hydrogel according to claim 1, which is characterized in that the grafting rate of the polylysine is 10% ~ 45%.
3. hydrogel according to claim 1, which is characterized in that the molecular weight of the polylysine is 3000 ~ 5000 Da.
4. hydrogel according to claim 1, which is characterized in that the tensile elongation of the hydrogel is 1000% ~ 2500%,
Saturated water absorption is 400% ~ 800%.
5. the preparation method of any one of claim 1 ~ 4 hydrogel, which is characterized in that the preparation method includes following step
Suddenly：
S1：1- (3- dimethylamino-propyls) -3- ethyl carbodiimides are added into polylysine aqueous solution（EDC）With N- hydroxyl ambers
Amber acid imide（NHS）, dialyse after reacting 4 ~ 8h, solution is lyophilized up to modified polylysine after taking dialysis；
S2：Addition acrylamide monomer is stirred after modified polylysine obtained by S1 is dissolved in water, and light is added after mixing
Initiator ammonium persulfate and N, N '-methylene-bisacrylamides continue ultraviolet light after stirring；
S3：Then it is 8 ~ 10 to adjust pH, is stood to get the hydrogel.
6. the preparation method of hydrogel according to claim 5, which is characterized in that the mass ratio of EDC described in S1 and NHS is
1:1~1:5, the mass ratio of the quality sum and polylysine of the EDC and NHS is 5:100~10:100；Preferably, the EDC
Mass ratio with NHS is 1:1.
7. the preparation method of hydrogel according to claim 5, which is characterized in that modified polylysine described in S2 is dissolved in water
Mass concentration afterwards is 10 ~ 20%；The mass ratio of the modified polylysine and acrylamide monomer is 1:10~10:1, preferably
1:1。
8. the preparation method of hydrogel according to claim 5, which is characterized in that ammonium persulfate and N in S2, N '-methylene
The mass ratio of bisacrylamide is 1:1；Ammonium persulfate and N, the quality sum and acrylamide of N '-methylene-bisacrylamides
The mass ratio of monomer is 1:100~5:100.
9. the preparation method of hydrogel according to claim 5, which is characterized in that pH is adjusted to 9 in S3.
10. any one of claim 1 ~ 4 hydrogel is preparing chronic wound reparation closure product, diabetes reparation product
Or surgical wound surface repairs the application in product.
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