CN101564400A - Antibacterial supermolecule aquogel and preparation method and application thereof - Google Patents
Antibacterial supermolecule aquogel and preparation method and application thereof Download PDFInfo
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- CN101564400A CN101564400A CNA200910039822XA CN200910039822A CN101564400A CN 101564400 A CN101564400 A CN 101564400A CN A200910039822X A CNA200910039822X A CN A200910039822XA CN 200910039822 A CN200910039822 A CN 200910039822A CN 101564400 A CN101564400 A CN 101564400A
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Abstract
The invention discloses a method for in-situ preparing antibacterial supermolecule aquogel. The method comprises the following operation steps: silver nitrate crystal and polyethyleneglycol-polypropylene glycol-polyethyleneglycol triblock copolymer solution are mixed and stirred to obtain mixed solution; the steps of stirring the mixed solution for 15 minutes and ultrasonically dispersing the mixed solution for 5 minutes are alternatively carried out for 2-4 hours to obtain nano silver sol; and the nano silver sol and Alpha-cyclodextrin solution are mixed, stirred and stands at the room temperature to obtain hydrogel. The hydrogel can be used for preparing injectable drug carriers. The invention has the advantages of simple operation, adjustable gel strength and the gelation time, room temperature forming, no involvement of chemical cross linking reaction and the usage of organic solvent, favorable biocompatibility and antibacterial property of obtained gel, and the like and is prospective to be widely applied in the field of biomedical engineering materials.
Description
Technical field
The invention belongs to the bio-medical engineering material field, particularly a kind of antibacterial supermolecule aquogel and its production and application.
Background technology
Receive much concern because of its potential application based on cyclodextrin, the supramolecular structured hydrogel that forms by Subjective and Objective assembling effect in fields such as organizational project, pharmaceutical carrier and controlled releases.This gellike material be contain the Polyethylene Glycol segment by a cyclodextrin and a class polymer by host-guest interaction, the gel rubber material that assembling forms with supramolecular structure.Its preparation condition gentleness, lower to temperature and concentration requirement, do not relate to organic solvent, sol-gel is reversible, and can be used as load and release that the novel injectable gel of a class is applied to drug molecule.Simultaneously, on the cyclodextrin molecular a large amount of hydroxyl for the further functionalization of material provides may.Recently, the functional nano particle is doped in a class hybrid gel material that forms in the middle of the gel network and has caused people's extensive concern.The introducing of functional nano particle not only can be regulated the physical-mechanical properties of gel, and can give gel new functionalization, has expanded the application of gel greatly.
Nanometer silver is considered to a kind of nontoxic, environment-friendly material, and has good antibacterial property, is widely used in the various antibiotic preparations.In actual applications, utilize the carrier and the excipient effect of hydrogel, nanometer silver is scattered in the polymer gel network, obtained a series of gel rubber materials that possess antibacterial functions.(Polymer such as Geckeler, 2007,48:158-164) at first prepared the gel network that PNIPAM and sodium polyacrylate are cross-linked to form by chemical reaction, then gel is immersed swelling in the silver nitrate solution, after treating that gel network absorption silver nitrate reaches poised state, again it is immersed in the sodium borohydride solution and reduce, finally obtained possessing the hybrid gel material of antibacterial functions.But there is chemical reaction in the forming process of this gellike, causes the residual of organic molecule in the material easily and then causes the bio-toxicity of material; The preparation of nano silver colloidal sol also is by sodium borohydride reduction, has caused the residual of inorganic salt by-product equally inevitably.The disclosed preparation method that contains the nano silver antimicrobial gel preparation of Chinese invention patent CN 101062055A, at first obtain nanometer silver with vitamin C reduction silver nitrate solution, utilize nano silicon to be carrier then, the nanometer silver that has prepared is carried on silica surface, has obtained nano silver colloidal sol; Again this colloidal sol is mixed with a certain proportion of carbomer excipient such as (carbomer), obtained containing the antibacterial gel preparation of nanometer silver.Though the residual of chemical by-product avoided in the formation of this gellike, have that the nano-Ag particles particle size distribution obtain is wide, the preparation of gel shortcomings such as higher and step is various to conditional requests such as concentration, temperature.
Polymer P luronic is the trade name of class Polyethylene Glycol-polypropylene glycol-Polyethylene Glycol (PEO-PPO-PEO) triblock polymer, having excellent biological compatibility, is one of minority synthetic compound of being can be used as medicine and food additive by drugs approved by FDA.Utilize Pluronic polymer self to the reduction of silver nitrate and to the stably dispersing effect of nanometer silver, can in aqueous solution, original position make nano silver colloidal sol; And then by itself and the host-guest interaction of cyclodextrin, the formation supramolecular structured hydrogel.Up to now, the host-guest interaction in-situ preparing by polymer and cyclodextrin contains the antibacterial gel of nanometer silver and uses and do not appear in the newspapers as yet.The method is expected to improve the dispersion and the stability thereof of nanometer silver, and has avoided chemical reaction, is expected to be widely used at biomedical engineering field.
Summary of the invention
For solving the weak point that prior art exists, primary and foremost purpose of the present invention is to provide a kind of method of in-situ preparing antibacterial supermolecule aquogel.
Another object of the present invention is to provide a kind of hydrogel of method for preparing.
A further object of the present invention is to provide the application of above-mentioned hydrogel in biomedical material engineering field.
Purpose of the present invention is achieved through the following technical solutions: a kind of method of in-situ preparing antibacterial supermolecule aquogel comprises following operating procedure:
(1) at room temperature, 1.0～10.0mg silver nitrate crystal is joined in polyethylene glycol-propylene glycol-Polyethylene Glycol (PEO-PPO-PEO) triblock copolymer solution that the 1.0mL mass percentage concentration is 5.0%～20% (w/w), under stirring condition, make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution was hocketed 2～4 hours according to stirring 15 minutes, 5 minutes step of ultra-sonic dispersion, obtain the nano silver colloidal sol of polymer reduction, stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is the alpha-cyclodextrin solution of 10%～20% (w/w), mixes, and leaves standstill under the room temperature, obtains hydrogel.
Step (1)～(3) described room temperature is 5～35 ℃.
The molecular weight of the described polyethylene glycol-propylene glycol of step (1)-Polyethylene Glycol triblock copolymer is 6000～15000, and wherein the ethylene glycol unit accounts for 57%～85% of ethylene glycol unit and propylene glycol unit sum.
The described polyethylene glycol-propylene glycol-industrialized Pluronic series of the optional usefulness of Polyethylene Glycol triblock copolymer, common Pluronic model comprises F-68 (EO
76-PO
29-EO
76), F-127 (EO
100-PO
65-EO
100) etc.
The described polyethylene glycol-propylene glycol of step (1)-Polyethylene Glycol triblock copolymer solution is that polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer is dissolved in water or the buffer reagent; The described alpha-cyclodextrin solution of step (3) is that alpha-cyclodextrin is dissolved in water or the buffer reagent; Described buffer reagent is succinate or citrate.
The mixing speed of the described stirring of step (2) is 300～900 rev/mins; The supersonic frequency of described ultra-sonic dispersion is 50～90KHz.
The described time of leaving standstill of step (3) is 6～12 hours.
A kind of antibacterial supermolecule aquogel according to method for preparing.
The application of above-mentioned antibacterial supermolecule aquogel in the preparation injectable drug carriers.
Principle of the present invention is: the present invention at first utilizes the reduction of polyethylene glycol-propylene glycol-Polyethylene Glycol (PEO-PPO-PEO) triblock copolymer self, reduces silver nitrate in aqueous solution, has obtained the nano silver colloidal sol of stably dispersing; And then the Subjective and Objective assembling of passing through PEO-PPO-PEO copolymer and alpha-cyclodextrin interacts, further obtained containing the supramolecular structured hydrogel of nanometer silver, the main active force that hydrogel forms is crystallization and the segmental hydrophobic interaction of polypropylene glycol after the cyclodextrin assembling.
The present invention has following advantage compared with prior art:
(1) preparation method of the present invention is simple, and is convenient to operation; Form under the room temperature, mild condition requires lower to concentration and temperature conditions;
(2) reaction system does not need additional reducing agent, but relies on the reduction of (PEO-PPO-PEO) triblock copolymer self, can avoid the residual of reduction reaction by-product effectively;
(3) network structure of gel is to rely on the crystallization of cyclodextrin and the physical actions such as hydrophobic interaction power between the polymer to form, and can avoid the bio-toxicity that remaining small molecule by-product may cause behind the chemical crosslink reaction effectively;
(4) intensity of gel and gelation time can be regulated and control by polymer concentration, and along with the increase of polymer concentration, the elastic modelling quantity of gel increases, and gelation time shortens;
(5) nanometer silver at first forms the colloidal sol of stably dispersing by means of polymer in aqueous solution, and then utilizes sol-gel technique, and the Subjective and Objective assembling effect by polymer and cyclodextrin is doped in the gel-type vehicle; This preparation method has guaranteed the homodisperse of nano-Ag particles in gel-type vehicle, still gives the supermolecular gel good antibacterial performance under the lower condition of silver content;
(6) polymer plays the multiple action of Reducing agent, dispersion stabilizer and gel-type vehicle in system, can simplify gel formula, saves cost;
(7) hydrogel component of the present invention is simple, good biocompatibility, and anti-microbial property is good, possesses the characteristic of good shear shinning, uses convenient and swiftly, is expected to be widely used in the bio-medical engineering material field as injectable pharmaceutical carrier.
Description of drawings
Fig. 1 is the wide-angle x-ray diffraction pattern spectrogram of supermolecular gel.
Fig. 2 is the transmitance curve chart over time of nano silver colloidal sol.
Fig. 3 is the transmission electron microscope picture of nano silver colloidal sol.
Fig. 4 is the sem photograph that contains the hydridization supermolecular gel of nanometer silver.
Fig. 5 is the change curve of hydridization supermolecular gel viscosity with shear rate.
Fig. 6 is a supermolecular gel to colibacillary bacteriostatic experiment figure as a result.
The specific embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but embodiments of the present invention are not limited thereto.
(1) under 25 ℃ of room temperatures, get 0.05g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.95g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution solution of 5%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 300 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 90KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel A.
Embodiment 2:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 300 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 90KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel B.
Embodiment 3:
(1) under 25 ℃ of room temperatures, get 0.20g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.80g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 20%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 300 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 90KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel C.
Embodiment 4:
(1) under 35 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 300 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 90KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 5:
(1) under 5 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 300 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 90KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 6:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 1.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 300 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 90KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 7:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 10.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 300 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 90KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 8:
(1) under 10 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g sodium succinate reagent, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 900 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 50KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 9:
(1) under 25 ℃ of room temperatures, it is soluble in water to get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-127), is made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 900 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 50KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 10:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-127) and be dissolved in the 0.90g sodium succinate reagent, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 600 rev/mins magnetic agitation 15 minutes, hocketed 2 hours with 5 minutes step of 70KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 11:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 600 rev/mins magnetic agitation 15 minutes, hocketed 4 hours with 5 minutes step of 70KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 15% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 6 hours, obtains injectable hydridization supermolecular gel.
Embodiment 12:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-127) and be dissolved in the 0.90g sodium citrate buffer reagent, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 5.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 600 rev/mins magnetic agitation 15 minutes, hocketed 3 hours with 5 minutes step of 70KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 10% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 8 hours, obtains injectable hydridization supermolecular gel.
Embodiment 13:
(1) under 20 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g water, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 8.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 700 rev/mins magnetic agitation 15 minutes, hocketed 4 hours with 5 minutes step of 80KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 20% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 12 hours, obtains injectable hydridization supermolecular gel.
Embodiment 14:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g sodium succinate buffer reagent, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 3.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 600 rev/mins magnetic agitation 15 minutes, hocketed 3 hours with 5 minutes step of 70KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 17% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 10 hours, obtains injectable hydridization supermolecular gel.
Embodiment 15:
(1) under 25 ℃ of room temperatures, get 0.10g polyethylene glycol-propylene glycol-Polyethylene Glycol (PluronicF-68) and be dissolved in the 0.90g sodium citrate buffer reagent, be made into polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 10%; The 3.0mg silver nitrate crystal is joined in the above-mentioned copolymer solution of 1.0mL, stir and make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution is 600 rev/mins magnetic agitation 15 minutes, hocketed 3 hours with 5 minutes step of 70KHz supersonic frequency ultra-sonic dispersion according to rotating speed, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 17% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature 10 hours, obtains injectable hydridization supermolecular gel.
Embodiment 16:
The supermolecular gel B that embodiment 2 is obtained carries out the wide-angle x-ray diffraction and measures, the result as shown in Figure 1, curve 1 is not for containing the supermolecular gel contrast of nanometer silver, curve 2 is supermolecular gel B of the present invention.From Fig. 1 as seen, there is tangible peak crystallization in supermolecular gel B of the present invention at 2 θ=19.8 degree places, this peak crystallization corresponding to alpha-cyclodextrin through the peak crystallization of " the accurate many rotaxanes " that form on the polymer chain (Macromolecules, 1990,23:2821-2823).In addition, also there is the characteristic diffraction peak of tangible nanocrystalline silver in the present invention supermolecular gel B of containing nanometer silver.
Embodiment 17:
Curve is (as shown in Figure 2 over time for the transmitance of step (2) the gained nano silver colloidal sol by ultraviolet-visible spectrophotometer tracking implementing example 1,2,3, line a, line b, line c correspond respectively to the nano silver colloidal sol among the embodiment 1,2,3) and the transmission electron microscope (as shown in Figure 3) of step (2) the gained nano silver colloidal sol of embodiment 2 characterize, discovery utilizes the reduction of polymer self and the dual function of stably dispersing, can obtain uniform particle diameter, finely disseminated nano silver colloidal sol, and polymer concentration is high more, and its stability is good more; Step (3) is carried out electron-microscope scanning by the hydridization supermolecular gel B that the sol-gel technique original position makes, the electron-microscope scanning picture as shown in Figure 4, visible nano-Ag particles is dispersed in the gel-type vehicle, and uniform particle diameter.
Embodiment 18:
Embodiment 19:
The bacteriostasis property result of table 1 antibacterial supermolecule gel
| Sample number into spectrum | Gel sample size (mm) | Antibacterial ring size (mm) |
| The supermolecular gel that does not add nanometer silver | 7 | 0 |
| A | 7 | 9.8 |
| B | 7 | 10.6 |
| C | 7 | 10.8 |
Annotate: the bacteriostatic test result is provided by Guangdong Province's microbiological analysis inspection center.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1, a kind of method of in-situ preparing antibacterial supermolecule aquogel is characterized in that comprising following operating procedure:
(1) at room temperature, it is in polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer solution of 5.0%～20% that 1.0～10.0mg silver nitrate crystal is joined the 1.0mL mass percentage concentration, under stirring condition, make dissolution of crystals, obtain the mixed solution of polymer and silver nitrate;
(2) at room temperature, step (1) gained mixed solution was hocketed 2～4 hours according to stirring 15 minutes, 5 minutes step of ultra-sonic dispersion, obtain the nano silver colloidal sol of stably dispersing;
(3) adding the 1.0mL mass percentage concentration in step (2) gained nano silver colloidal sol is 10%～20% alpha-cyclodextrin solution, mixes, and leaves standstill under the room temperature, obtains hydrogel.
2, the method for a kind of in-situ preparing antibacterial supermolecule aquogel according to claim 1 is characterized in that: step (1)～(3) described room temperature is 5～35 ℃.
3, the method for a kind of in-situ preparing antibacterial supermolecule aquogel according to claim 1, it is characterized in that: the molecular weight of the described polyethylene glycol-propylene glycol of step (1)-Polyethylene Glycol triblock copolymer is 6000～15000, and wherein the ethylene glycol unit accounts for 57%～85% of ethylene glycol unit and propylene glycol unit sum.
4, the method for a kind of in-situ preparing antibacterial supermolecule aquogel according to claim 1 is characterized in that: the described polyethylene glycol-propylene glycol of step (1)-Polyethylene Glycol triblock copolymer solution is that polyethylene glycol-propylene glycol-Polyethylene Glycol triblock copolymer is dissolved in water or the buffer reagent; The described alpha-cyclodextrin solution of step (3) is that alpha-cyclodextrin is dissolved in water or the buffer reagent.
5, the method for a kind of in-situ preparing antibacterial supermolecule aquogel according to claim 4 is characterized in that: described buffer reagent is succinate or citrate.
6, the method for a kind of in-situ preparing antibacterial supermolecule aquogel according to claim 1 is characterized in that: the mixing speed of the described stirring of step (2) is 300～900 rev/mins; The supersonic frequency of described ultra-sonic dispersion is 50～90KHz.
7, the method for a kind of in-situ preparing antibacterial supermolecule aquogel according to claim 1 is characterized in that: the described time of leaving standstill of step (3) is 6～12 hours.
8, a kind of hydrogel according to each described method preparation of claim 1～7.
9, the application of hydrogel according to claim 8 in the preparation injectable drug carriers.
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