CN110433316A - A kind of photo-thermal/ion Synergistic antimicrobial hydrogel and its preparation method and application - Google Patents
A kind of photo-thermal/ion Synergistic antimicrobial hydrogel and its preparation method and application Download PDFInfo
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Abstract
The present invention provides a kind of photo-thermal/ion Synergistic antimicrobial hydrogel and its preparation method and application, it is related to a kind of poly-dopamine/mix copper bioactive ceramics composition, the raw material composition of the poly-dopamine/mix copper bioactive ceramics composition includes: modification polyglutamic acid water-soluble polymers by dopamine and adipic dihydrazide graft modification and mixes copper bioactive ceramics powder；Wherein, the mass percent concentration of the modified polyglutamic acid water-soluble polymers is 2.5%~10%, and the additional amount for mixing copper bioactive ceramics powder is the 0.5%~5% of the quality of the modified polyglutamic acid water-soluble polymers.
Description
Technical field
The present invention relates to a kind of photo-thermal/ion Synergistic antimicrobial hydrogel and its preparation method and application, belong to it is biomedical,
Material technology, wound repair and medical instruments field.
Background technique
The wound as caused by fire, mechanical accident, disease etc. easily infects, and wound suppuration is caused to fester, it is difficult to it heals,
Considerable distress is caused to patient.How to accomplish efficiently to remove existing infection, and inhibit the growth of bacterium in a long time, simultaneously
Promotion Healing can be played to the large area surface of a wound, is of great significance to the treatment of the infection type surface of a wound, us is worth to go to visit
Rope innovation.
Inorganic metal ion, such as copper ion can inhibit the growth of various bacteria for a long time, also have very to some drug-fast bacterias
Good lethal effect, but copper ion and bacterium need longer action time to can be only achieved bactericidal effect, take effect relatively slow.Photo-thermal is anti-
Bacterium material can use the high temperature of near infrared light generation, quickly, effectively kill all kinds of bacteriums on surface, and antibacterial is quick,
It is high-efficient.But photo-thermal anti-biotic material, which exists, removes the deficiency that bacterium after high temperature easily breeds repeatedly, is unable to reach long-acting, stable anti-
Bacterium effect.Meanwhile two class anti-biotic material all there is a problem of that biocompatibility is insufficient.Theoretically copper ion concentration is higher, photo-thermal
The temperature of generation is higher, and antibacterial effect is better.But in fact, when copper ion concentration is excessively high, toxicity can be generated to cell and tissue,
The thermogenetic high temperature of crossing of light also can generate injury to surrounding tissue.Also, after infection removal, the quick reparation problem of the surface of a wound
Also it is not resolved.
Summary of the invention
On the one hand the present inventor recognizes that dopamine is a kind of neurotransmitter of human body, oxygen can occur under alkaline condition
Change autohemagglutination and generates the poly-dopamine with photo-thermal effect.On the other hand it recognizes, mixes copper bioactive ceramics (for example, mixing copper silicon
Sour calcium mixes copper bio-vitric, mixes copper calcium phosphate, mixes copper hydroxyapatite etc.), it can degrade in water, generate alkaline ring
Border simultaneously discharges copper ion and silicon ion.The copper ion of release is able to suppress bacterial multiplication, while silicon ion promotees jointly with copper ion
Into angiogenesis, be conducive to the reparative regeneration of wound tissue.And complexing can occur for copper ion and dopamine.Based on this,
It is an object of that present invention to provide a kind of dopamine and mix the interaction of copper calcium silicates and quick removing infection and long acting antibiotic
Composite hydrogel (as dressing presence) and its preparation method and application.
In a first aspect, the present invention provides a kind of poly-dopamines/mix copper bioactive ceramics composition, the poly- DOPA
The raw material composition of amine/mix copper bioactive ceramics composition includes: the poly- paddy of modification by dopamine and adipic dihydrazide graft modification
Propylhomoserin water-soluble polymers and mix copper bioactive ceramics powder；Wherein, the modified polyglutamic acid water-soluble polymers
Mass percent concentration is 2.5%~10%, and the additional amount for mixing copper bioactive ceramics powder is the modified polyglutamic
The 0.5%~5% of the quality of sour water-soluble polymers.
To mix copper calcium silicates as an example, the interaction for mixing copper calcium silicates and dopamine is embodied in two aspects a: side
Due to mixing copper calcium silicates, quick ion exchange will cause the change of pH microenvironment in aqueous solution in face, and alkalinity is presented.It therefore can
With the oxidation for being used to stimulate dopamine using the alkaline signal that copper calcium silicates discharges in aqueous solution is mixed, the poly-dopamine of generation can
As photo-thermal preparation.Meanwhile the copper ion in aqueous solution and the poly-dopamine of generation generate complexing, reinforce system crosslinking.
Second aspect, the present invention provides a kind of poly-dopamine/copper complex, the poly-dopamine/copper complex passes through
Following methods preparation:
(1) alkaline solution is added in the modification polyglutamic acid water-soluble polymers by dopamine and adipic dihydrazide graft modification
Afterwards, mixed solution is obtained；
(2) isometric copper ion solution is added in gained mixed solution, and complex reaction occurs, obtains the poly- DOPA
Amine/copper complex；Wherein, the mass percent concentration of the modified polyglutamic acid water-soluble polymers is 2.5%~10%；Institute
Stating alkaline solution is 0.5~2M NaOH solution, and additional amount is the quality of the modified polyglutamic acid water-soluble polymers
5%~15%；The copper ion solution is the aqueous solution of standard copper ion, and concentration is no more than 1000ppm；Preferably, the copper
The concentration of solion is 1~1000ppm, more preferably 1~50ppm.
The third aspect, the present invention provides a kind of poly-dopamine/bioactive ceramics composite hydrogel, the poly- DOPA
Amine/bioactive ceramics composite hydrogel raw material composition includes: the poly- paddy of modification by dopamine and adipic dihydrazide graft modification
Propylhomoserin water-soluble polymers mix copper bioactive ceramics powder, glutamic acid and oxidized dextran aqueous solution；Wherein, described to change
Property polyglutamic acid water-soluble polymers mass percent concentration be 2.5%~10%, it is described to mix copper bioactive ceramics powder
Additional amount be the modified polyglutamic acid water-soluble polymers quality 0.5%~5%；The additional amount of the glutamic acid is
Mix the 40%~60% of copper bioactive ceramics powder quality, preferably 50%；The quality percentage of the oxidized dextran aqueous solution
Specific concentration is 2.5%~10%；The volume ratio of the modified polyglutamic acid water-soluble polymers and oxidized dextran aqueous solution is
1:(0.5~1.5), preferably 1:1.
Preferably, the modified polyglutamic acid macromolecule is by being grafted dopamine and adipic dihydrazide using amide reaction
It is formed in polyglutamic acid high polymer long chain, wherein dopamine, adipic dihydrazide and the high molecular molar ratio of polyglutamic acid are
(0.05~0.2): (0.5~1.5): 1, preferably 0.1:1:1.
Preferably, it is described mix copper bioactive ceramics powder be selected from mix copper bio-vitric, mix copper calcium phosphate, mix copper hydroxyl phosphorus
Lime stone and mix at least one of copper calcium silicates；The doping for mixing copper in copper bioactive ceramics powder be 1wt%~
20wt%, preferably 5wt%.
Preferably, the particle scale for mixing copper bioactive ceramics powder is 71 μm or less.
In the present invention, to mix copper calcium silicates as an example, the presence for mixing copper calcium silicates keeps poly-dopamine/mix copper biology living
Property ceramic composition pH stable in strong basicity range, by acidic amino acid glutamic acid strong basicity can be adjusted to alkalescent or
It is neutral.The chemical bonding of the aldehyde groups of hydrazides group and oxidized dextran based on modified polyglutamic acid, generates and is based on acylhydrazone
The composite hydrogel of key.
Preferably, the mass ratio of glucan and sodium metaperiodate is 0.2:1 or 0.4:1 when preparing oxidized dextran.Preferably
0.4:1。
Fourth aspect, the present invention provides a kind of antibiotic methods, using the above-mentioned poly-dopamine/bioactivity of laser irradiation
Ceramic Composite hydrogel makes while its heating and discharges copper ion, to realize Synergistic antimicrobial；Preferably, the wave of the laser
A length of 808nm, power 0.41W/cm2~1.21W/cm2。
5th aspect, the present invention provides a kind of above-mentioned poly-dopamine/bioactive ceramics composite hydrogels to prepare
Application in infection type wound repair material.
Detailed description of the invention
Fig. 1 is the plastic photo of poly-dopamine/mix copper calcium silicates composite hydrogel；
Fig. 2 is to verify dopamine and mix the interaction diagram of copper calcium silicates, wherein a) generates alkaline environment to mix copper calcium silicates, makes
Dopamine oxidation；B) Cu ion and Si ion are discharged to mix copper calcium silicates；The poly-dopamine of generation is complexed with copper ion, institute
Solution colour d) and absorbance c) is obtained to change；
Fig. 3 is poly-dopamine/copper complex solution light thermal property enhancing schematic diagram after complexing Cu ion, a) is the light of copper ion
Heating curve, b) it is poly-dopamine and the photo-thermal curve after copper ion complexing；
Fig. 4 be mix copper calcium silicates hydrogel (Cu) and complexing formed poly-dopamine/mix copper calcium silicates composite hydrogel (P/Cu)
Anti-microbial property schematic diagram a) can to the biocompatibility c) of fibroblastic biocompatibility schematic diagram b) and endothelial cell
To find out that material anti-microbial property and biocompatibility are improved；
Fig. 5 shows the in vitro vascularized performance map for the different hydrogels that complexing is formed, it can be seen that can further promote external
Vascularization；
Fig. 6 is the photo-thermal of poly-dopamine/mix copper calcium silicates hydrogel (P/Cu or PDA/Cu-CS) and control group hydrogel (Ctrl)
Performance characterization: wherein a) being REAL TIME INFRARED THERMAL IMAGE thermal image；It b) is different hydrogel sample photo-thermal curves；It c) is different ceramic contents
Poly-dopamine/mix copper calcium silicates hydrogel photo-thermal curve；D) for different laser powers poly-dopamine/mix copper calcium silicates hydrogel
Photo-thermal curve；It e) is poly-dopamine/mix copper calcium silicates hydrogel continuous warming-cooling photo-thermal curve, it can be seen that poly-dopamine/
It is excellent to mix copper calcium silicates hydrogel light thermal property, and there is photo and thermal stability, Ceramic Composite amount and laser power can also be passed through
Adjust photo-thermal curve；
Fig. 7 is poly-dopamine/mix copper calcium silicates hydrogel active ion release performance characterization: a) being laser light photograph-not illumination 8h
Plasma diffusing W,Mo comparison；It b) is the plasma diffusing W,Mo research of hydrogel under 15min laser irradiation short-term (15min) and long-term (12h)；c)
For composite hydrogel degradation plasma diffusing W,Mo research in 7 days；The result shows that hydrogel can continue to release for a long time copper ion and silicon from
Son, and plasma diffusing W,Mo can be regulated and controled by laser irradiation；
Fig. 8 is that there is poly-dopamine/mix copper calcium silicates hydrogel excellent anti-microbial property to characterize, and a) is wherein poly-dopamine/mix
Copper calcium silicates composite hydrogel colony counting method the anti-bacterial result, b) and c) for bacteriostasis rate count, it is known that hydrogel can quickly and
Long-acting inhibition bacterium；
Fig. 9 is facilitation of poly-dopamine/the mix copper calcium silicates hydrogel to fibroblast a) and endothelial cell b) proliferation.
Figure 10 is poly-dopamine/mix copper calcium silicates hydrogel to the fungistatic effect of the rat In vivo infection type surface of a wound, wherein a) is the 8th
It when rat trauma surface infestation situation comparison diagram；B) it is counted for different time sections rat surface of a wound bacteriostasis rate, it can be seen that compound water congealing
Glue has best killing effect under laser irradiation auxiliary, to the bacterium at trauma surface infestation, and (wherein-Blank is represented to infection
For the type surface of a wound without using material as negative control group ,+Blank representative uses commercial antimicrobial ointment Ciprofloxacin Hydrochloride element as face
According to)；
Figure 11 shows poly-dopamine/mix copper calcium silicates hydrogel to rat In vivo infection type wound repair as a result, different time
Section rat surface of a wound digital photograph a) and wound healing percentage b)；
Figure 12 is different time sections poly-dopamine/mix copper calcium silicates hydrogel to the surface of a wound group of rat In vivo infection type wound repair
Knit H&E coloration result；
Figure 13 is different time sections poly-dopamine/mix copper calcium silicates hydrogel to the surface of a wound group of rat In vivo infection type wound repair
Knit CD31 coloration result；
Figure 14 is different time sections poly-dopamine/mix copper calcium silicates hydrogel to the surface of a wound group of rat In vivo infection type wound repair
The number of blood vessel knitted counts a) the diameter distribution statistics b) with the vessel size of wound tissue at the 8th day；
Figure 15 is different time sections poly-dopamine/mix copper calcium silicates hydrogel to the surface of a wound group of rat In vivo infection type wound repair
Knit I coloration result of COLL-.
Specific embodiment
The present invention is further illustrated below by way of following embodiments, it should be appreciated that following embodiments are merely to illustrate this
Invention, is not intended to limit the present invention.
In the disclosure, poly-dopamine/mix copper silicic acid calcium composition, comprising: the modification of grafting dopamine and adipic dihydrazide
Polyglutamic acid water-soluble polymers and mix copper calcium silicate powder.Wherein, it is grafted the modification polyglutamic acid of dopamine and adipic dihydrazide
Macromolecule and the content for mixing copper calcium silicate powder are respectively (2.5%~10wt%) and (0.5%~5wt%).It should be understood that this is more
The above-mentioned each component of bar amine/mix copper calcium silicates can completely or partially separate or mixed form presence.It is more in this system
Bar amine interacts with copper calcium silicates is mixed.For example, the interaction for mixing copper calcium silicates and dopamine shows and mixes copper silicic acid
Calcium generates the oxidation autohemagglutination that alkaline environment promotes dopamine, generates poly-dopamine.Meanwhile the copper ion in aqueous solution and generate
Poly-dopamine generates complexing, reinforces system crosslinking.
Fig. 2, which is shown as being added in the modification polyglutamic acid Polymer Solution of grafting dopamine, mixes copper calcium silicates, solution
PH value reaches 11~12 in 1min, shows strong basicity.And copper ion and silicon ion can be largely discharged in 1min.With
The increase of copper calcium silicates compound quantity, the alkalinity enhancing of solution are mixed, the release of copper ion and silicon ion increases.It is high to modified polyglutamic acid
100 μ L 1M NaOH are added in molecular solution, form poly-dopamine solution.In poly-dopamine solution be added various concentration copper from
After sub- solution, the lighter of mixed liquor, absorbance changes, and shows that poly-dopamine is complexed with copper ion.
In alternative embodiments, poly-dopamine/mix in copper silicic acid calcium composition, the macromolecule (grafting containing dopamine
The modification polyglutamic acid macromolecule of dopamine and adipic dihydrazide), to mix the mass ratio of copper calcium silicates can be (2.5%~10%):
(0.5%~5%).Here " 0.5~5% " refer to 0.5% or more, 5% hereinafter, include 0.5% and 5%.Mix copper calcium silicates
Middle Copper-cladding Aluminum Bar amount be 1%~20wt%, preferably 5%.It mixes copper calcium silicate particle and crosses 200 meshes, scale is 71 μm or less.It is excellent
Choosing, mixing copper calcium silicates, compound quantity is up to 5wt% in the composition.
In alternative embodiments, when progress polyglutamic acid is modified, dopamine and polyglutamic acid molar ratio are 0.1:1,
Adipic dihydrazide and polyglutamic acid molar ratio are 1:1, and the modification polyglutamic acid high score of grafting dopamine and adipic dihydrazide is prepared
Son.
It should be understood that poly-dopamine/mix mixed in copper silicic acid calcium composition copper calcium silicates can further be chosen as mixing copper biology it is living
Property ceramics, preparation poly-dopamine/mix copper bioactive ceramics composition.For example, mixing copper bioactive ceramics can also be to mix copper life
Object glass mixes copper calcium phosphate, mixes copper hydroxyapatite etc..
On the other hand the present invention also provides poly-dopamine/copper complexs, at least by grafting dopamine and adipic dihydrazide
Modification polyglutamic acid water-soluble polymers (such as concentration 5%), alkaline solution and copper ion solution, obtained after complex reaction.
Wherein, copper ion solution is copper ion standard solution 1000ppm (1.000g/L) (for example, buying from Shanghai City metrology and measurement skill
Art research institute, model GBW (E) 08027).Various concentration copper ion solution is to dilute copper ion standard solution, example with ultrapure water
Such as, 0,1,20,50,500,1000ppm etc..The additional amount of copper ion solution and gathered by the modification of grafting dopamine and adipic dihydrazide
Glutamic acid water-soluble polymers are identical as the total volume of the mixed solution of alkaline solution.The alkaline solution is 0.5~2M NaOH
Solution, additional amount are the 5%~15% of the quality of the modified polyglutamic acid water-soluble polymers.In this system, gather more
Bar amine/copper complex promotes the light thermal property enhancing of poly-dopamine solution.Specifically, network occurs for poly-dopamine and copper ion
It closes, enhance the light thermal property of compound while making the anti-microbial property and fibroblast and endothelial cell proliferation of hydrogel
Can, it enhance in vitro at vascular performance.
After Fig. 3 shows that poly-dopamine solution is mixed with copper ion solution, since poly-dopamine and copper ion are complexed, mixed liquor
Light thermal property improve, temperature change be greater than poly-dopamine solution and aqueous solution mixed liquor.When copper ion concentration is greater than
When 1000ppm, due to copper ion excess, the active site of poly-dopamine is occupied by copper ion, and mixed liquor light thermal property reduces.And
Copper ions alone solution, light thermal property is very weak, and when concentration is greater than 1000ppm or more, temperature only increases 4~5 DEG C when 5min.
Fig. 4~Fig. 5 is shown, due to the complexing of poly-dopamine and copper ion, poly-dopamine/mix copper calcium silicates composite hydrogel
(P/Cu) copper calcium silicates hydrogel (Cu) is mixed compared to copper ions alone effect, bacteriostasis property improves, to fibroblast and interior
The biocompatibility of chrotoplast improves, and more culture endothelial cells can be promoted at blood vessel.
In the disclosure, with poly-dopamine/mix copper calcium silicates composite hydrogel as an example, be described in detail preparation method and
Using.The composite hydrogel is based on dopamine and to mix the interaction of copper calcium silicates and modified polyglutamic acid and oxidized dextran
Crosslinking is prepared.Poly-dopamine/mix copper calcium silicates composite hydrogel, due to poly-dopamine/copper complex formazan effect, antibiotic property
Energy, fibroblast are compared with endothelial cell proliferation performance, in vitro at vascular performance compared with copper ion, hence it is evident that enhancing.
Poly-dopamine/mix copper calcium silicates composite hydrogel at least by mixing copper calcium silicates, containing dopamine and hydrazides group
Modified polyglutamic acid (referred to as modified polyglutamic acid), the oxidized dextran containing aldehyde radical, adjust pH glutamic acid mixing plastic and
.The composite hydrogel further includes that (concentration is oxidized dextran aqueous solution in addition to poly-dopamine/mix copper silicic acid calcium composition
2.5%~10wt%), glutamic acid adjusts pH range, and modified polyglutamic acid and oxidized dextran form acylhydrazone hydrogel.It is modified poly-
The gross mass content score of glutamic acid and oxidized dextran can be 2.5%~10%, preferably 5%.As a poly-dopamine/
The example of copper calcium silicates composite hydrogel prepared in detail is mixed, including；Modified polyglutamic acid aqueous solution is configured, copper silicic acid is mixed in addition
Calcium powder body is mixed to get mixed solution.Wherein the mass concentration of modified polyglutamic acid is 2.5%~10% in mixed solution, mixes copper
The mass concentration of calcium silicates is 0.5~5%, preferably 0.5~2%, more preferably 2%.Glutamic acid is added and adjusts solution ph
It is mixed for neutral or alkalescent (pH=7~8), then the oxidized dextran solution for being 2.5%~10% with mass fraction, certain
Time in gel in-situ, obtain the composite hydrogel.Wherein the volume ratio of mixed solution and oxidized dextran solution is 1:
(0.5~1.5).
The above-mentioned poly-dopamine of present invention offer/mix copper calcium silicates composite hydrogel using photo-thermal/ion synergistic effect, is realized
A kind of quick and long-acting antibiotic method.808nm laser illumination hydrogel 15min is first used, high temperature (45 DEG C of >) was generated
Bacterium is killed, recycles hydrogel to discharge the further bacteriostatic proliferation of copper ion for a long time, prevents bacterium from breeding repeatedly.Laser
Power be 0.41W/cm2~1.21W/cm2, preferably 0.8W/cm2.The concentration range of copper ion release is 1~5 μ g/mL, excellent
It is selected as 1~3 μ g/mL.
In the present invention, above-mentioned poly-dopamine/mix copper calcium silicates composite hydrogel is in vivo in infection type skin wound healing
Application.
In the present invention, the performance detection of poly-dopamine/mix copper calcium silicates composite hydrogel.
Light thermal property detection: utilizing 808nm near infrared light hydrogel, is become using thermal imaging system real time monitoring temperature
Change, obtains heating image and curve.
Plasma diffusing W,Mo detection: freshly prepared composite hydrogel is immersed in ultrapure water, carries out continuous laser photograph respectively
It penetrates, without laser irradiation, it is separately sampled every a hour in 8h and supplement new liquid.Freshly prepared composite hydrogel is impregnated
In ultrapure water, 15min laser irradiation is carried out respectively, without laser irradiation, it is separately sampled in 15min and 12h and supplement new liquid.
Freshly prepared composite hydrogel is immersed in ultrapure water, respectively at the 1st day, samples and supplements new liquid within 3 days, 5 days and 7 days.
Use Cu and Si ion concentration in inductive coupling plasma emission spectrograph (ICP-AES) Test extraction liquid.
In-vitro antibacterial detection: the 500 freshly prepared composite hydrogels of μ L are placed in 5mL centrifuge tube, are added thereto
1mL 106CFU·mL-1Escherichia coli bacteria liquid is placed in 37 DEG C, 120rpm shakes after 808nm laser irradiation hydrogel 15min
12h is cultivated in bed, and coated plate after ten thousand times of dilution counts after cultivating 15h in 37 DEG C of biochemical cultivation cases.500 μ L are freshly prepared multiple
Heshui gel is placed in 5mL centrifuge tube, and 1mL 10 is added thereto6CFU·mL-1Escherichia coli bacteria liquid uses 808nm laser
After irradiating hydrogel 30min, 37 DEG C are placed in, 1.5h is cultivated in 120rpm shaking table, 30min laser irradiation-is carried out continuously in 8h
The operation that 1.5h is normally cultivated, coated plate after inoculum in different time periods is diluted ten thousand times are trained in 37 DEG C of biochemical cultivation cases
It is counted after supporting 15h.
Cell in vitro proliferation detection: the freshly prepared composite hydrogel of 1mL is placed in 15mL centrifuge tube, is added
10mLDMEM high glucose medium or ECM culture medium, prepare composite hydrogel leaching liquor.Leaching liquor is sterilized using 0.22 μm of mycoderm
Processing is separately added into 10% serum and 1% dual anti-, stand-by for gradient dilution with 1/2.Every hole kind into 96 porocyte culture plates
1000 cells, the cell culture medium before being replaced afterwards using the leaching liquor of gradient dilution for 24 hours, are cultivated 1 day, 3 days and 5 days respectively
Cck-8 test fluid is added afterwards, surveys the OD value at 450nm.
Internal antibacterial effect: the round surface of a wound for being 15mm in SD rat back manufacture diameter, and infect 100 μ L 3 ×
109CFU·mL-1Escherichia coli bacteria liquid.After infection for 24 hours, poly-dopamine/mix copper calcium silicates composite hydrogel is applied, is used in combination
808nm laser irradiates 15min every other day.On day 4, the 8th day, diffusate at the surface of a wound is taken with sterile swab within the 14th day, be placed in bacterium
After expanding 4h in culture medium, dilutes ten thousand times of coated plates and count.
In-vivo tissue repairing effect: on day 4, the 8th day, taking pictures to wound tissue on the 14th day, counts wound healing
Rate.I dyeing of H&E, CD31 and COLL- processing is carried out after taking wound tissue to be fixed with paraformaldehyde, observation surface of a wound regional organization is raw
Long situation.
Enumerate embodiment further below with the present invention will be described in detail.It will similarly be understood that following embodiment is served only for this
Invention is further described, and should not be understood as limiting the scope of the invention, those skilled in the art is according to this hair
Some nonessential modifications and adaptations that bright above content is made all belong to the scope of protection of the present invention.Following examples are specific
Technological parameter etc. is also only an example in OK range, i.e. those skilled in the art can be done properly by the explanation of this paper
In the range of select, and do not really want to be defined in hereafter exemplary specific value.
1 poly-dopamine of embodiment/mix copper silicic acid calcium composition
(1) it is reacted using amide and dopamine and adipic dihydrazide is grafted in polyglutamic acid high polymer long chain, and it is modified to prepare 5%
Polyglutamic acid solution；
(2) copper calcium silicate powder will be mixed to be added in modified polyglutamic acid solution, and be uniformly mixed, poly-dopamine/mix copper silicon is obtained
Sour calcium composition.Poly-dopamine/mix mixed in copper silicic acid calcium composition copper calcium silicate powder mass fraction be respectively 0.5%, 1%,
2%, 5%.
Dopamine interacts with copper calcium silicates is mixed in this system: it is more to mix the generation alkaline environment promotion of copper calcium silicates
The oxidation of bar amine, meanwhile, the poly-dopamine of copper ion and generation in aqueous solution generates complexing.
(a) and (b) in Fig. 2 make dopamine oxygen the result shows that alkaline environment can be generated and discharge ion by mixing copper calcium silicates
Change；The poly-dopamine of generation with can be complexed with the copper ion of release.
2 poly-dopamine of embodiment/copper complex formazan preparation
(1) it is reacted using amide and dopamine and adipic dihydrazide is grafted in polyglutamic acid high polymer long chain, and it is modified to prepare 5%
Polyglutamic acid solution；
(2) 10wt%1M NaOH solution (100 μ L) is added into 5% modified polyglutamic acid solution (0.5mL), forms poly- DOPA
Amine aqueous solution；
(3) be separately added into in poly-dopamine solution (0.5mL) 0.5mL 0,1,20,50,500,1000ppm copper ion solution
(GBW (E) 08027, Shanghai Institute of Measurement and Testing Technology) forms poly-dopamine/copper complex.
In Fig. 2 (c) and (d) the result shows that the poly-dopamine that generates and after copper ion is complexed, solution colour and extinction
Degree changes.Fig. 3 result illustrates the light thermal property enhancing of solution after complexing.
3 poly-dopamine of embodiment/mix copper calcium silicates composite hydrogel (P/Cu)
(1) it is reacted using amide and dopamine and adipic dihydrazide is grafted in polyglutamic acid high polymer long chain, and it is modified to prepare 5%
Polyglutamic acid solution；
(2) the high molecular vicinal diamines structure of sodium periodate oxidation glucan is utilized, the oxidized dextran with aldehyde radical is prepared and is matched
Set 5% solution；
(3) copper calcium silicates is mixed by 0.5%, 1%, 2% and 5% to be separately added into modified polyglutamic acid solution, and be uniformly mixed.
It by mass fraction is respectively again later to mix 1/2 glutamic acid of copper calcium silicates mass fraction to be added in modified polyglutamic acid solution,
Adjusting pH is neutral or alkalescent；
(4) be added configured isometric oxidized dextran solution into mixed liquor again, in certain time can plastic, obtain
Poly-dopamine/mix copper calcium silicates composite hydrogel.
It will be seen from figure 1 that be added 2% mix copper calcium silicates after, modified polyglutamic acid solution becomes black from light yellow, more
Bar amine aoxidizes.After glutamic acid and oxidized dextran is added, colloid is become from solution, is inverted does not flow in test tube.
Fig. 4 and Fig. 5 shows the complexing due to poly-dopamine and copper ion, so that hydrogel (Fig. 4 and Fig. 5 after complexing
Middle hydrogel P/Cu, which is generally, is added 2% hydrogel for mixing copper calcium silicates) anti-microbial property enhancing, to fibroblast and endothelium
The biocompatibility of cell improves, and promotes in vitro vascularized further enhance.
4 control group hydrogel (Ctrl) of embodiment
(1) it is reacted using amide and adipic dihydrazide is grafted in polyglutamic acid high polymer long chain, and prepare the modified poly- paddy of 5% hydrazides
Propylhomoserin solution；
(2) the high molecular vicinal diamines structure of sodium periodate oxidation glucan is utilized, the oxidized dextran with aldehyde radical is prepared and is matched
Set 5% solution；
(3) mixing hydrazides is modified polyglutamic acid solution and oxidized dextran solution in equal volume, can plastic in certain time.
5 poly-dopamine hydrogel (PDA) of embodiment
(1) it is reacted using amide and dopamine and adipic dihydrazide is grafted in polyglutamic acid high polymer long chain, and it is modified to prepare 5%
Polyglutamic acid solution；
(2) the high molecular vicinal diamines structure of sodium periodate oxidation glucan is utilized, the oxidized dextran with aldehyde radical is prepared and is matched
Set 5% solution；
(3) 10%1M NaOH solution is added into 5% modified polyglutamic acid solution, and 1% glutamic acid is added and adjusts pH, formed
Poly-dopamine solution；
(4) mixing hydrazides is modified polyglutamic acid solution and oxidized dextran solution in equal volume, can plastic in certain time.
Embodiment 6 mixes copper calcium silicates hydrogel (Cu)
(1) it is reacted using amide and adipic dihydrazide is grafted in polyglutamic acid high polymer long chain, and prepare 5% hydrazides polyglutamic acid
Solution；
(2) the high molecular vicinal diamines structure of sodium periodate oxidation glucan is utilized, the oxidized dextran with aldehyde radical is prepared and is matched
Set 5% solution；
(3) 2% is added into 5% hydrazides polyglutamic acid solution and mixes copper calcium silicates powder, and 1% glutamic acid is added and adjusts solution
pH；
(4) polyglutamic acid solution and oxidized dextran solution for mixing copper calcium silicates is added in isometric mixing, and certain time is interior
Plastic.
Poly-dopamine/mix copper calcium silicates composite hydrogel with photo-thermal/ion synergetic antibacterial effect, can be realized inside and outside
Quick and durable antibacterial effect.Poly-dopamine disclosed herein/mix copper calcium silicates hydrogel, can be with good light thermal property
High temperature is generated under 808nm laser irradiation, quickly kills bacterium.And composite hydrogel disclosed herein being capable of sustained release life
Object active ion can use the long-acting inhibition bacterium of copper ion of release.Research poly-dopamine/mix copper calcium silicates combination laser photograph
(P+I) is penetrated in the repairing effect of the infection type surface of a wound, with poly-dopamine hydrogel combination laser irradiation (P), independent poly-dopamine/mix
Copper calcium silicates composite hydrogel (I), the vitro antibacterial activity of independent control group hydrogel (Ctrl).Fig. 3~Fig. 5 verifies poly- DOPA
After amine and copper ion complexing, the raising of material property.
Fig. 6 the results show that composite hydrogel in a very short period of time, temperature significantly increases, have good light thermal property.It is logical
Change is crossed to mix copper calcium silicates compound quantity, laser power etc. and can regulate and control the light thermal property of composite hydrogel.To hydrogel into
Row laser irradiation heats up-closes the circulate operation of laser Temperature fall, and hydrogel still keeps good light thermal property, illustrates water-setting
Glue has photo and thermal stability.
Fig. 7 the result shows that poly-dopamine/mix copper calcium silicates composite hydrogel (2% mixes copper calcium silicates) and fast long-acting can release
The property let live copper ion and silicon ion, and laser irradiation has facilitation to the release of copper ion and silicon ion.And it is short-term
The influence that (15min) laser irradiation generates long-term (> 12h) plasma diffusing W,Mo is smaller.
Fig. 8 the result shows that, poly-dopamine/mix copper calcium silicates composite hydrogel (2% mixes copper calcium silicates) to Escherichia coli
Inhibition has the characteristics that quick and durable, and bacteriostasis rate highest.With simple copper ion (I) compared with simple photo-thermal (P), photo-thermal with from
When sub- collective effect (P+I), it can be rapidly achieved fungistatic effect, and bacteriostasis rate is maintained at 98% or more.
Fig. 9 the result shows that, by after poly-dopamine/mix copper calcium silicates composite hydrogel (2% mixes copper calcium silicates) gradient dilution,
Have the function of promoting proliferation to fibroblast and endothelial cell in very big concentration range.
The internal antibacterial and repairing effect of the invention hydrogel are assessed using rat back infection type wound model.Research
Poly-dopamine/mix copper calcium silicates combination laser irradiation (P+I) is cementing with poly-dopamine water-setting in the repairing effect of the infection type surface of a wound
It closes laser irradiation (P), independent poly-dopamine/mix copper calcium silicates composite hydrogel (I), independent control group hydrogel (Ctrl), no
Rat back infection type is created using material (- Blank) and using clinical antimicrobial Ciprofloxacin Hydrochloride plain (+Blank)
The antibacterial and repair in face.
Figure 10 the result shows that, using poly-dopamine/mix copper calcium silicates composite hydrogel (2% mixes copper calcium silicates) in conjunction with laser
It irradiates (photo-thermal is cooperateed with ion, P+I), fungistatic effect is best.Figure 11-12 result can be seen that P+I group, and wound healing is most fast.
Figure 13-14 the result shows that, P+I group new vessels number is most, and new vessels diameter is generally greater than other components.Figure 15 result can
To find out P+I group, newborn region collagen staining is most deep, collagen distribution.From Figure 11-15 the result shows that, poly-dopamine/mix copper silicic acid
Calcium composite hydrogel (2% mixes copper calcium silicates) can be obviously promoted the reparation of the infection type surface of a wound, the surface of a wound in conjunction with laser irradiation (P+I)
Minimum, new vessels are most, and collagen arrangement is most.
Claims (11)
1. a kind of poly-dopamine/mix copper bioactive ceramics composition, which is characterized in that the poly-dopamine/mix the work of copper biology
Property ceramic composition raw material composition include: water-soluble by dopamine and the modification polyglutamic acid macromolecule of adipic dihydrazide graft modification
Liquid and mix copper bioactive ceramics powder；Wherein, the mass percent concentration of the modified polyglutamic acid water-soluble polymers
It is 2.5%~10%, the additional amount for mixing copper bioactive ceramics powder is the modified polyglutamic acid water-soluble polymers
The 0.5%~5% of quality.
2. poly-dopamine according to claim 1/mix copper bioactive ceramics composition, which is characterized in that the modification
Polyglutamic acid macromolecule is that dopamine and adipic dihydrazide are grafted in polyglutamic acid high polymer long chain by being reacted using amide
It is formed, wherein dopamine, adipic dihydrazide and the high molecular molar ratio of polyglutamic acid are (0.05~0.2): (0.5~1.5): 1,
It is preferred that 0.1:1:1.
3. poly-dopamine according to claim 1 or 2/mix copper bioactive ceramics composition, which is characterized in that described to mix
Copper bioactive ceramics powder is selected from mixing copper bio-vitric, mix copper calcium phosphate, mix copper hydroxyapatite and mix in copper calcium silicates
It is at least one；The doping for mixing copper in copper bioactive ceramics powder is 1wt %~20wt%, preferably 5wt %.
4. poly-dopamine according to any one of claim 1-3/mix copper bioactive ceramics composition, feature exists
In the particle scale for mixing copper bioactive ceramics powder is 71 μm or less.
5. a kind of poly-dopamine/copper complex, which is characterized in that the poly-dopamine/copper complex is prepared by following methods:
(1) alkaline solution is added in the modification polyglutamic acid water-soluble polymers by dopamine and adipic dihydrazide graft modification
Afterwards, mixed solution is obtained；
(2) isometric copper ion solution is added in gained mixed solution, and complex reaction occurs, obtains the poly- DOPA
Amine/copper complex；Wherein, the mass percent concentration of the modified polyglutamic acid water-soluble polymers is 2.5%~10%；It is described
Alkaline solution be 0.5~2M NaOH solution, additional amount be the modified polyglutamic acid water-soluble polymers quality 5%~
15%；The copper ion solution is the aqueous solution of standard copper ion, and concentration is no more than 1000ppm；Preferably, the copper ion is molten
The concentration of liquid is 1~1000ppm, more preferably 1~50ppm.
6. poly-dopamine/copper complex according to claim 5, which is characterized in that the modified polyglutamic acid macromolecule
It is the wherein DOPA by dopamine and adipic dihydrazide being grafted in polyglutamic acid high polymer long chain being formed using amide reaction
Amine, adipic dihydrazide and the high molecular molar ratio of polyglutamic acid are (0.05~0.2): (0.5~1.5): 1, preferably 0.1:1:1.
7. a kind of poly-dopamine/bioactive ceramics composite hydrogel, which is characterized in that the poly-dopamine/bioactivity pottery
The raw material composition of porcelain composite hydrogel includes: water-soluble by dopamine and the modification polyglutamic acid macromolecule of adipic dihydrazide graft modification
Liquid mixes copper bioactive ceramics powder, glutamic acid and oxidized dextran aqueous solution；Wherein, the modified polyglutamic acid high score
The mass percent concentration of sub- aqueous solution is 2.5%~10%, and the additional amount for mixing copper bioactive ceramics powder is described changes
The 0.5%~5% of the quality of property polyglutamic acid water-soluble polymers；The additional amount of the glutamic acid is to mix copper bioactive ceramics powder
The 40%~60% of weight, preferably 50%；The mass percent concentration of the oxidized dextran aqueous solution is 2.5%~10%；It is described
The volume ratio of modified polyglutamic acid water-soluble polymers and oxidized dextran aqueous solution is 1:(0.5~1.5), preferably 1:1.
8. poly-dopamine according to claim 7/bioactive ceramics composite hydrogel, which is characterized in that the modification
Polyglutamic acid macromolecule is that dopamine and adipic dihydrazide are grafted in polyglutamic acid high polymer long chain by being reacted using amide
It is formed, wherein dopamine, adipic dihydrazide and the high molecular molar ratio of polyglutamic acid are (0.05~0.2): (0.5~1.5): 1,
It is preferred that 0.1:1:1.
9. poly-dopamine according to claim 7 or 8/bioactive ceramics composite hydrogel, which is characterized in that described to mix
Copper bioactive ceramics powder is selected from mixing copper bio-vitric, mix copper calcium phosphate, mix copper hydroxyapatite and mix in copper calcium silicates
It is at least one；The doping for mixing copper in copper bioactive ceramics powder is 1wt%~20wt%, preferably 5wt %.
10. the poly-dopamine according to any one of claim 7-9/bioactive ceramics composite hydrogel, feature exist
In the particle scale for mixing copper bioactive ceramics powder is 71 μm or less.
11. poly-dopamine/bioactive ceramics composite hydrogel described in a kind of any one of claim 7-10 is felt in preparation
Application in dye type wound repair material.
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