CN104971376B - Types of Medicine elastomer wound dressing and preparation method thereof is carried containing halloysite nanotubes - Google Patents

Types of Medicine elastomer wound dressing and preparation method thereof is carried containing halloysite nanotubes Download PDF

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CN104971376B
CN104971376B CN201510366367.XA CN201510366367A CN104971376B CN 104971376 B CN104971376 B CN 104971376B CN 201510366367 A CN201510366367 A CN 201510366367A CN 104971376 B CN104971376 B CN 104971376B
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halloysite nanotubes
antibacterials
medicine
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elastomer
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CN104971376A (en
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张立群
牛玉昭
薛佳佳
廖美红
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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Abstract

The present invention relates to carry Types of Medicine elastomer wound dressing and preparation method thereof containing halloysite nanotubes.It is, using degradable natural polymer as matrix, and to add and antibacterials and be loaded with the halloysite nanotubes of antibacterials, passes through and heats blending and prepare the elastomer biomembrane with different bioactivity.Material price of the present invention is cheap, with excellent biological property and degradability, simultaneously also can promotion organization Regeneration and Repair, insoluble drug release may also suppress incident bacterium infection and inflammation, can be widely applied to the medicine and hygiene fieldses such as organizational project medium-height trestle, artificial organs, wound dressing, medicine fixed point release film, blood storage bag and medical catheter.

Description

Types of Medicine elastomer wound dressing and preparation method thereof is carried containing halloysite nanotubes
Technical field:
The invention belongs to bioabsorbable polymer material field, and in particular to it is a kind of using degradable natural macromolecular material as Matrix material simultaneously adds antibacterials and is loaded with the wound dressing elastomer biomembrane and its system of the halloysite nanotubes of antibacterials Preparation Method.
Background technology:
Skin is the barrier contacted with external environment, it is easy to injured or because disease etc. causes defect of skin, and this can lead Moisture, electrolyte and the protein loss of the surface of a wound are caused, the open surface of a wound also add the probability of infection.
It is general that wound is covered and protected using dressing and is provided with beneficial to wound healing in order to slow down the generation of above-mentioned symptom Environment.For a comparatively long period of time, the use of most common surgical wound dressings is medical absorbent cotton and gauze.It is to wound Treatment can play certain facilitation, but there is very big deficiency.For example it is in use, wound granulation tissue is to dressing It is interior growth and cause adhesion;During releasing, secondary insult is easily caused;Bacterium infection is easily caused due to surface of a wound hydrops.Therefore, develop A kind of new pattern compress, makes it can not only flap coverage, moreover it is possible to help wound healing sealing point and body fluid to escape and absorb from the surface of a wound The diffusate flowed out from the surface of a wound, prevents bacteria attack, reduces superelevation metabolism and the malnutrition of wound area, nontoxic sterile, plus Fast wound healing, with certain pliability and intensity, promotes the growth of new skin, into one of main direction of scientific research personnel.
Biological dressing arises at the historic moment as a kind of new medical wound dressing.It is usually directly to utilize native organism Material, such as:The autologous skin of human body, other animal allograft skins, deep-sea plant, or utilize the derivative of biomaterial.Biological dressing It is good with human compatibility that advantage is mainly, and toxic side effect is small, antigenicity is low, has certain water penetration, can reduce the dressing of the surface of a wound Number of times, the infection for reducing colony density and favorably controlling section, are also effectively reduced the physical damnification of new raw meat dental tissue.And And, antibacterials are added in natural biologic material, more effectively can quickly suppress the growth of bacterium colony and the generation of inflammation, profit In the recovery of the surface of a wound.
Halloysite nanotubes are a kind of aluminosilicates of tubulose, and its external diameter is about 50-80nm, and internal diameter is about 10- 15nm, length is about 1000nm, and load factor is about 15%-20%.Halloysite nanotubes have natural origin, will not be to ring Border is polluted, and with good biocompatibility.
The content of the invention
The present invention adds antibacterials in system and is loaded with the halloysite nanotubes of antibacterials, and preparation, which contains, carries Types of Medicine Elastomer biomembrane.If having higher requirement to the degradation rate or mechanical property and water resistance of obtained biomembrane, The biomembrane can also be crosslinked.
Types of Medicine elastomer wound dressing is carried containing halloysite nanotubes, it is characterized in that including:
The material formed by hot melt using degradable natural polymer and plasticizer adds antibacterial as matrix material Medicine and the halloysite nanotubes for being loaded with antibacterials;
The mass ratio of natural polymer and plasticizer is 100:50~100:1000, natural polymer and it is loaded with antibacterials Halloysite nanotubes mass ratio be 100:5~100:50, wherein halloysite nanotubes used are carried out with silane coupler It was modified, the quality for being loaded with the halloysite nanotubes of antibacterials is gross mass of the halloysite nanotubes with being loaded into medicine, can be dropped The ratio of antibacterials quality of the natural polymer gross mass of solution with being directly loaded into matrix is 100:1~100:50.
Further, degradable natural macromolecular material is:In gelatin, collagen, chitosan, sodium alginate, elastin laminin One or more kinds of mixtures.
Further, the plasticizer is any one of following material or two or more mixtures:Glycerine, water, second Glycol.
Further, antibacterials, comprising penicillins, cephalosporin class, Tetracyclines, chloromycetin, macrolide, Lincomycin, fluoroquinolones, nitro glyoxaline and/or polypeptide antimicrobial;Antibacterials are loaded into halloysite nanotubes, then will The halloysite nanotubes for carrying medicine are added in matrix by Haake mode, another part medicine are directly added into the base, directly Add some drugs in matrix with loading galapectite pipe medicine is identical or difference.
The described preparation method that Types of Medicine elastomer wound dressing is carried containing halloysite nanotubes, it is characterised in that including under Step:
(1) by mass ratio 100:50~100:1000 natural polymer is added in reactor with plasticizer, 50~ 90 DEG C reaction 2~10 days after take out, obtain elastomer rubber;
(2) antibacterials A is added in its good solvent, its dissolving is obtained its saturated solution by ultrasonic agitation;
(3) halloysite nanotubes are modified with silane coupler;
(4) halloysite nanotubes being modified and the saturated solution of above-mentioned preparation is taken to mix, ultrasound obtains scattered angstrom The suspension of Lip river stone nanotube;Suspension is vacuumized until liquid surface is centrifuged after occurring there is no bubble, after centrifugation Solution cleaned with the good solvent of antibacterials removing precipitation, you can obtain being loaded with the halloysite nanotubes of antibacterials;
(5) the above-mentioned halloysite nanotubes for being loaded with antibacterials A are dried, and it is ground to form powder;
(6) halloysite nanotubes and antibacterials B that are loaded with antibacterials A are added into the above-mentioned elastomer prepared to give birth to In glue, the method for kneading blending by Haake is combined, and mixing time is 15~40min, and rotating speed is 30~80r/min, temperature Spend for 40 DEG C~80 DEG C, be made and carry Types of Medicine bioelastomer containing halloysite nanotubes;Wherein, natural polymer is with being loaded with antibacterial The mass ratio of medicine A halloysite nanotubes is 100:5~100:50, the mass ratio of natural polymer and antibacterials B is 100:1~100:50;
(7) by the above-mentioned bioelastomer prepared tabletting on vacuum tablet press machine, temperature is 45 DEG C~70 DEG C, and tabletting is total Time is 15min~40min, prepares and carries Types of Medicine elastomer biomembrane containing halloysite nanotubes.
Further, the good solvent of described antibacterials be water, ethanol, acetone, toluene, hexafluoroisopropanol, trifluoroethanol, One or more of mixed solvents in chloroform, methanol, dichloromethane, N, N '-dimethyl formamide.
Further, silane coupler, including 3- aminopropyl triethoxysilanes, γ-(2,3- the third oxygen of epoxy) propyl group front three One kind in TMOS.
Further, obtained elastomer biomembrane is immersed in the ethanol for the crosslinking agent that mass concentration is 0.01%-10% 10min-12h is crosslinked in solution, immersion is embathed 1-10 times respectively after terminating in ethanol and deionized water, by biomembrane in ventilation Room temperature is placed 1-7 days in cupboard.
Further, crosslinking agent, including formaldehyde, glutaraldehyde, Geniposide, 1- ethyls -3- (3- dimethyl aminopropyls)-carbonization two One kind in imines (EDC), n-hydroxysuccinimide (NHS).
The load medicine of this material is divided into two parts, and a part is the antibacterials being directly present in matrix, another part It is present in halloysite nanotubes.It is present in the antibacterials in biomembrane and first diffuses to matrix surface and is then transferred to pars affecta Position, slow down the speed of insoluble drug release, alleviates phenomenon of burst release, also effectively inhibits the generation of inflammation.
Brief description of the drawings
Fig. 1 is the antibacterials Ciprofloxacin and not that gelatin matrix carrier prepared by the inventive method has same amount The correlation of the elastomer biomembrane of the halloysite nanotubes (HNT) (5%-15% mass ratioes) of same amount antibacterials polymyxin B The naming method of sample is in implementation result figure, picture:G50 represents that the mass ratio of gelatin and water is 100:50.C1 represents elasticity The total mass ratio of Ciprofloxacin containing antibacterials and gelatin is 1% in body biomembrane.H5 represents to contain antibacterial in elastomer biomembrane The halloysite nanotubes of medicine polymyxin B and the total mass ratio of gelatin are that 5%, H10 represents to contain antibacterial in elastomer biomembrane The halloysite nanotubes of medicine polymyxin B and the total mass ratio of gelatin are that 10%, H15 represents to contain antibacterial in elastomer biomembrane The halloysite nanotubes of medicine polymyxin B and the total mass ratio of gelatin are 15%.
It is the drug release patterns of antibacterial drug Ciprofloxacin in above-mentioned G50C1HNT elastomers biomembrane.
Fig. 2-(1), Fig. 2-(2) are the antibacterials rings that gelatin matrix carrier prepared by the inventive method has same amount The elastomer of the halloysite nanotubes (HNT) (10%-50% mass ratioes) of third husky star and non-same amount antibacterials cephalosporin The naming method of sample is in the related implementation result figure of biomembrane, picture:G500 represents that the mass ratio of gelatin and glycerine is 100:500.C50 represents that the total mass ratio of Ciprofloxacin containing antibacterials and gelatin in elastomer biomembrane is 50%.H10 is represented The total mass ratio of the halloysite nanotubes of the cephalosporin containing antibacterials and gelatin is that 10%, H50 is represented in elastomer biomembrane The total mass ratio of the halloysite nanotubes of the cephalosporin containing antibacterials and gelatin is 50%, other samples in elastomer biomembrane Analogize.
Fig. 2-(1) is the degraded figure line of above-mentioned G500C50HNT elastomers biomembrane.
Fig. 2-(2) are the water suction figure lines of above-mentioned G500C50HNT elastomers biomembrane.
Fig. 3-(1), Fig. 3-(2) are the antibacterials that gelatin matrix carrier prepared by the inventive method has same amount The bullet of the halloysite nanotubes (HNT) (0%-20% mass ratioes) of quadracycline and non-same amount antibacterials quadracycline The naming method of sample is in the related implementation result figure of property body biomembrane, picture:G100 represents the mass ratio of gelatin and glycerine For 100:100.T15 represents that the total mass ratio of quadracycline containing antibacterials and gelatin in elastomer biomembrane is 10%.H0 The total mass ratio for representing the halloysite nanotubes of the quadracycline containing antibacterials and gelatin in elastomer biomembrane is 0%, H20 The total mass ratio for representing the halloysite nanotubes of the quadracycline containing antibacterials and gelatin in elastomer biomembrane is 20%, its He analogizes at sample.
Fig. 3-(1) is the medicine of antibacterials quadracycline in above-mentioned G150T15HNT elastomers biomembrane galapectite pipe Release profiles.
Fig. 3-(2) are the cytotoxicity experiment results of above-mentioned G150T15HNT elastomers biomembrane.
Fig. 4-(1), Fig. 4-(2) are the antibacterials rings that gelatin matrix carrier prepared by the inventive method has same amount The elastomer of third husky star and the halloysite nanotubes (HNT) (0%-20% mass ratioes) of non-same amount antibacterials polymyxin B The naming method of sample is in the related implementation result figure of biomembrane, picture:G150 represents that the mass ratio of gelatin and glycerine is 100:150.C10 represents that the total mass ratio of Ciprofloxacin containing antibacterials and gelatin in elastomer biomembrane is 10%.H0 is represented The total mass ratio of the halloysite nanotubes of the polymyxin B containing antibacterials and gelatin is that 0%, H20 is represented in elastomer biomembrane The total mass ratio of the halloysite nanotubes of the polymyxin B containing antibacterials and gelatin is 20%, other samples in elastomer biomembrane Category is pushed away.
Fig. 4-(1) is the drug release patterns of antibacterial drug Ciprofloxacin in above-mentioned G150C10HNT elastomers biomembrane.
Fig. 4-(2) are the medicines of antibacterials polymyxin B in above-mentioned G150C10HNT elastomers biomembrane galapectite pipe Release profiles.
Embodiment:
The present invention is further illustrated below by embodiment, but the present invention is not limited to these examples.Specific effect is such as Shown in brief description of the drawings.
Example 1:100:50:5:1
(1) 32.05g gelatin and 16.03g water are added in reaction flask, are put into after stirring in vacuum drying oven, temperature is set 70 DEG C are set to, question response takes out after 7 days and obtains required uniform elastomer rubber.
(2) 2g halloysite nanotubes are weighed to be put into three-necked flask and add 20ml toluene reagents, are filled into three-necked flask Nitrogen, oil bath pan sets temperature to be 120 DEG C, and after temperature rises to 120 DEG C, 4ml 3- ammonia third is continuously added into three-necked flask Ethyl triethoxy silicane alkane is modified the toluene solution that halloysite nanotubes are taken out after reaction, reaction 24h.It will be received containing galapectite The toluene solution of mitron is centrifuged, after centrifuging 5 times, and the halloysite nanotubes being modified are dried, grinding.
(3) 2g antibacterials aerosporins are weighed to be added in deionized water, are sufficiently stirred for making it dissolve and obtain The saturated solution of aerosporin.
(4) halloysite nanotubes that 1.8g has been modified are taken to be mixed with above-mentioned saturated solution, ultrasonic disperse obtains galapectite and received The suspension of mitron;Suspension is vacuumized, until the surface of solution is there is no bubble appearance, supernatant is taken out, spends Ionized water cleaning precipitation, repeats vacuum step 3 times, you can obtain being loaded with the halloysite nanotubes of aerosporin;Will be upper State and be loaded with the halloysite nanotubes of aerosporin and be dried, grind.
(5) above-mentioned 48.08g rubbers are taken to be loaded with the halloysite nanotubes of aerosporin in Haake mixing instrument with 1.6g Upper blending 10min, temperature setting is 45 DEG C, and rotating speed is 50r/min.Then 0.32g antibacterials Ciprofloxacins are added, are continued altogether Mixed 10min, takes out, what is kneaded is loaded with the glue of antibacterials.
(6) take the above-mentioned glue prepared of 10g to be placed on vacuum tablet press machine and be cold-pressed 15min at room temperature, drive the gas in glue away Bubble, it is 55 degree then to set temperature, carries out hot pressing 10min, obtains thickness and contains halloysite nanotubes for 1mm uniform bubble-frees Load Types of Medicine elastomer film.
Example 2:100:1000:50:50
(1) 4.17g gelatin and 41.67g glycerine are added in reaction flask, are put into after stirring in vacuum drying oven, temperature 50 DEG C are set to, question response takes out after 2 days and obtains required uniform elastomer rubber.
(2) weigh 2.5g halloysite nanotubes to be put into three-necked flask and add 30ml toluene reagents, into three-necked flask Inflated with nitrogen, oil bath pan sets temperature to be 120 DEG C, and after temperature rises to 120 DEG C, 5ml 3- ammonia is continuously added into three-necked flask Propyl-triethoxysilicane is modified the toluene solution that halloysite nanotubes are taken out after reaction, reaction 24h.Angstrom Lip river will be contained The toluene solution of stone nanotube is centrifuged, after centrifuging 5 times, and the halloysite nanotubes being modified are dried, grinding.
(3) 2.5g antibacterials cephalosporins are weighed to be added in deionized water, are sufficiently stirred for making it dissolve and obtain to the end The saturated solution of p0-357.
(4) halloysite nanotubes that 2.3g has been modified are taken to be mixed with the above-mentioned saturated solution containing cephalosporin, ultrasound point Dissipate the suspension for obtaining halloysite nanotubes;Suspension is vacuumized, until the surface of solution takes there is no bubble appearance Go out supernatant, precipitation is cleaned with deionized water, repeat vacuum step 3 times, you can the galapectite for obtaining being loaded with cephalosporin is received Mitron;The above-mentioned halloysite nanotubes for being loaded with cephalosporin are dried, ground.
(5) above-mentioned 45.84g rubbers are taken to be loaded with the halloysite nanotubes of cephalosporin in common on Haake mixing instrument with 2.08g Mixed 10min, temperature setting is 50 DEG C, and rotating speed is 70r/min.Then 2.08g antibacterials Ciprofloxacins are added, continue to be blended 10min takes out, and what is kneaded is loaded with the glue of antibacterials.
(6) take the above-mentioned glue prepared of 10g to be placed on vacuum tablet press machine and be cold-pressed 15min at room temperature, drive the gas in glue away Steep, it is 50 degree then to set temperature, carries out hot pressing 10min, obtain thickness and contain galapectite nanometer for 1.5mm uniform bubble-frees The load Types of Medicine elastomer film of pipe.
Example 3:100:100:15:10
(1) 22.22g sodium alginates and 11.11g glycerine and 11.11g deionized waters are added in reaction flask, stirred It is put into after mixing in vacuum drying oven, temperature setting is 60 DEG C, question response takes out after 5 days and obtains required uniform elastomer rubber.
(2) 4g halloysite nanotubes are weighed to be put into three-necked flask and add 40ml toluene reagents, are filled into three-necked flask Nitrogen, oil bath pan sets temperature to be 120 DEG C, and after temperature rises to 120 DEG C, 8ml 3- ammonia third is continuously added into three-necked flask Ethyl triethoxy silicane alkane is modified the toluene solution that halloysite nanotubes are taken out after reaction, reaction 24h.It will be received containing galapectite The toluene solution of mitron is centrifuged, after centrifuging 5 times, and the halloysite nanotubes being modified are dried, grinding.
(3) 4g antibacterials quadracyclines are weighed to be added in deionized water, are sufficiently stirred for dissolving it and obtaining salt The saturated solution of sour tetracycline.
(4) halloysite nanotubes that 3.5g has been modified are taken to be mixed with the above-mentioned saturated solution containing quadracycline, ultrasound The scattered suspension for obtaining halloysite nanotubes;Suspension is vacuumized, until the surface of solution is there is no bubble appearance, Supernatant is taken out, precipitation is cleaned with deionized water, vacuum step is repeated 3 times, you can obtains being loaded with the Ai Luo of quadracycline Stone nanotube;The above-mentioned halloysite nanotubes for being loaded with quadracycline are dried, ground.
(5) above-mentioned 44.44g rubbers are taken to be loaded with the halloysite nanotubes of quadracycline on Haake mixing instrument with 3.33g 10min is blended, temperature setting is 55 DEG C, and rotating speed is 70r/min.Then 2.22g antibacterials quadracyclines are added, are continued altogether Mixed 15min takes out, and what is kneaded is loaded with the glue of antibacterials.
(6) take the above-mentioned glue prepared of 10g to be placed on vacuum tablet press machine and be cold-pressed 15min at room temperature, drive the gas in glue away Bubble, it is 50 degree then to set temperature, carries out hot pressing 10min, obtains thickness and contains halloysite nanotubes for 2mm uniform bubble-frees Load Types of Medicine elastomer film.
Example 4:100:150:20:10
(1) 17.86g gelatin and 26.79g glycerine are added in reaction flask, are put into after stirring in vacuum drying oven, temperature 60 DEG C are set to, question response takes out after 7 days and obtains required uniform elastomer rubber.
(2) 4g halloysite nanotubes are weighed to be put into three-necked flask and add 40ml toluene reagents, are filled into three-necked flask Nitrogen, oil bath pan sets temperature to be 120 DEG C, and after temperature rises to 120 DEG C, 8ml 3- ammonia third is continuously added into three-necked flask Ethyl triethoxy silicane alkane is modified the toluene solution that halloysite nanotubes are taken out after reaction, reaction 24h.It will be received containing galapectite The toluene solution of mitron is centrifuged, after centrifuging 5 times, and the halloysite nanotubes being modified are dried, grinding.
(3) 4g antibacterials polymyxin Bs are weighed to be added in deionized water, are sufficiently stirred for making it dissolve and be glued more Rhzomorph B saturated solution.
(4) halloysite nanotubes that 3.8g has been modified are taken to be mixed with the above-mentioned saturated solution containing polymyxin B, ultrasound point Dissipate the suspension for obtaining halloysite nanotubes;Suspension is vacuumized, until the surface of solution takes there is no bubble appearance Go out supernatant, precipitation is cleaned with deionized water, repeat vacuum step 3 times, you can the galapectite for obtaining being loaded with polymyxin B is received Mitron;The above-mentioned halloysite nanotubes for being loaded with polymyxin B are dried, ground.
(5) above-mentioned 44.65g rubbers are taken to be loaded with the halloysite nanotubes of polymyxin B in common on Haake mixing instrument with 3.57g Mixed 20min, temperature setting is 55 DEG C, and rotating speed is 80r/min.Then 1.79g antibacterials Ciprofloxacins are added, continue to be blended 10min takes out, and what is kneaded is loaded with the glue of antibacterials.
(6) take the above-mentioned glue prepared of 10g to be placed on vacuum tablet press machine and be cold-pressed 15min at room temperature, drive the gas in glue away Bubble, it is 55 degree then to set temperature, carries out hot pressing 10min, obtains thickness and contains halloysite nanotubes for 1mm uniform bubble-frees Load Types of Medicine elastomer film.
(7) solution of crosslinking agent Geniposide is configured:3g Geniposides are weighed, are dissolved in 100ml ethanol solutions, Geniposide is molten Liquid concentration is 3%.
(8) the load Types of Medicine elastomer diaphragm containing halloysite nanotubes pressed is cut into 5cm*2cm rectangle, is immersed in Batten after crosslinking is used ethanol solution and deionization by Geniposide mass concentration respectively in 3% solution, to react at room temperature after 1h Water is respectively rinsed one time, places the load Types of Medicine elastomer film containing halloysite nanotubes for obtaining for 1 day being crosslinked.
Example 5:100:150:20:15
(1) 17.54g gelatin and 26.32g ethylene glycol are added in reaction flask, are put into after stirring in vacuum drying oven, temperature Degree is set to 60 DEG C, and question response takes out after 6 days and obtains required uniform elastomer rubber.
(2) 4g halloysite nanotubes are weighed to be put into three-necked flask and add 40ml toluene reagents, are filled into three-necked flask Nitrogen, oil bath pan sets temperature to be 120 DEG C, and after temperature rises to 120 DEG C, 8ml 3- ammonia third is continuously added into three-necked flask Ethyl triethoxy silicane alkane is modified the toluene solution that halloysite nanotubes are taken out after reaction, reaction 24h.It will be received containing galapectite The toluene solution of mitron is centrifuged, after centrifuging 5 times, and the halloysite nanotubes being modified are dried, grinding.
(3) 4g antibacterials Ciprofloxacins are weighed to be added in acetonitrile, are sufficiently stirred for dissolving it and obtaining Ciprofloxacin Saturated solution.
(4) halloysite nanotubes that 3.8g has been modified are taken to be mixed with the above-mentioned saturated solution containing Ciprofloxacin, ultrasound point Dissipate the suspension for obtaining halloysite nanotubes;Suspension is vacuumized, until the surface of solution is there is no bubble appearance, Supernatant is taken out, precipitation is cleaned with deionized water, vacuum step is repeated 3 times, you can obtains being loaded with the galapectite of Ciprofloxacin Nanotube;The above-mentioned halloysite nanotubes for being loaded with polymyxin B are dried, ground.
(5) above-mentioned 43.86g rubbers are taken to be loaded with the halloysite nanotubes of Ciprofloxacin in common on Haake mixing instrument with 3.51g Mixed 15min, temperature setting is 55 DEG C, and rotating speed is 80r/min.Then 2.63g antibacterials Ciprofloxacins are added, continue to be blended 15min takes out, and what is kneaded is loaded with the glue of antibacterials.
(6) take the above-mentioned glue prepared of 10g to be placed on vacuum tablet press machine and be cold-pressed 15min at room temperature, drive the gas in glue away Steep, it is 55 degree then to set temperature, carries out hot pressing 10min, obtain thickness and contain galapectite nanometer for 0.8mm uniform bubble-frees The load Types of Medicine elastomer film of pipe.
(7) solution of crosslinking agent Geniposide is configured:1g Geniposides are weighed, are dissolved in 100ml ethanol solutions, Geniposide is molten Liquid concentration is 1%.
(8) the load Types of Medicine elastomer diaphragm containing halloysite nanotubes pressed is cut into 5cm*2cm rectangle, is immersed in Batten after crosslinking is used ethanol solution and deionization by Geniposide mass concentration respectively in 1% solution, to react at room temperature after 2h Water is respectively rinsed one time, places the load Types of Medicine elastomer film containing halloysite nanotubes for obtaining for 7 days being crosslinked.

Claims (7)

1. Types of Medicine elastomer wound dressing is carried containing halloysite nanotubes, it is characterized in that including:
Degradable natural polymer and plasticizer are added in reactor, the material formed by hot melt is matrix material Material, and add antibacterials and be loaded with the halloysite nanotubes of antibacterials;The mass ratio of natural polymer and plasticizer is 100:50~100:1000, natural polymer and be loaded with antibacterials halloysite nanotubes mass ratio be 100:5~100: 50, wherein halloysite nanotubes used were modified with silane coupler, it is loaded with the halloysite nanotubes of antibacterials Quality is gross mass of the halloysite nanotubes with being loaded into medicine, and degradable natural polymer gross mass is with being directly loaded into matrix The ratio of antibacterials quality is 100:1~100:50;
Wherein described degradable natural macromolecular material is:One in gelatin, collagen, chitosan, sodium alginate, elastin laminin Plant or two or more mixtures;
The plasticizer is glycerine.
2. according to claim 1 carry Types of Medicine elastomer wound dressing containing halloysite nanotubes, it is characterized in that:Antimicrobial Thing, comprising penicillins, cephalosporin class, Tetracyclines, chloromycetin, macrolide, lincomycin, fluoroquinolones, Nitro glyoxaline and/or polypeptide antimicrobial;Antibacterials are loaded into halloysite nanotubes, then the halloysite nanotubes for carrying medicine are led to Cross Haake mode to be added in matrix, another part medicine is directly added into the base, be directly added into the part medicine in matrix Thing be loaded into halloysite nanotubes medicine is identical or difference.
3. the preparation method as claimed in claim 1 that Types of Medicine elastomer wound dressing is carried containing halloysite nanotubes, its feature It is to include lower step:
(1) by mass ratio 100:50~100:1000 natural polymer is added in reactor with plasticizer, at 50~90 DEG C Reaction is taken out after 2~10 days, obtains elastomer rubber;
(2) antibacterials A is added in its good solvent, its dissolving is obtained its saturated solution by ultrasonic agitation;
(3) halloysite nanotubes are modified with silane coupler;
(4) halloysite nanotubes being modified and the saturated solution of above-mentioned preparation is taken to mix, ultrasound obtains scattered galapectite The suspension of nanotube;Suspension is vacuumized and centrifuged after liquid surface occurs there is no bubble, it is molten after centrifugation Liquid cleans removing precipitation with antibacterials A good solvent, you can obtain being loaded with antibacterials A halloysite nanotubes;
(5) the above-mentioned halloysite nanotubes for being loaded with antibacterials A are dried, and it is ground to form powder;
(6) halloysite nanotubes and antibacterials B that are loaded with antibacterials A are added to the above-mentioned elastomer rubber prepared In, the method for kneading blending by Haake is combined, and mixing time is 15~40min, and rotating speed is 30~80r/min, temperature For 40 DEG C~80 DEG C, it is made and carries Types of Medicine bioelastomer containing halloysite nanotubes;Wherein, natural polymer is with being loaded with antimicrobial The mass ratio of thing A halloysite nanotubes is 100:5~100:50, natural polymer and antibacterials B mass ratio are 100:1 ~100:50;
(7) by the above-mentioned bioelastomer prepared tabletting on vacuum tablet press machine, temperature is 45 DEG C~70 DEG C, tabletting total time For 15min~40min, prepare and carry Types of Medicine elastomer biomembrane containing halloysite nanotubes.
4. method according to claim 3, it is characterized in that:Described antibacterials A good solvent be water, ethanol, acetone, One kind or several in toluene, hexafluoroisopropanol, trifluoroethanol, chloroform, methanol, dichloromethane, N, N '-dimethyl formamide Plant mixed solvent.
5. method according to claim 3, it is characterized in that:Silane coupler, including 3- aminopropyl triethoxysilanes, One kind in γ-(oxygen of 2,3- epoxies third) propyl trimethoxy silicane.
6. method according to claim 3, it is characterized in that:Obtained elastomer biomembrane is immersed in into mass concentration is 10min-12h is crosslinked in the ethanol solution of 0.01%-10% crosslinking agent, immersion is distinguished after terminating in ethanol and deionized water Embathe 1-10 times, by biomembrane, room temperature is placed 1-7 days in fume hood.
7. method according to claim 6, it is characterized in that:Crosslinking agent includes formaldehyde, glutaraldehyde, Geniposide, 1- ethyls -3- One kind in (3- dimethyl aminopropyls)-carbodiimides (EDC), n-hydroxysuccinimide (NHS).
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