CN104892842A - Antimicrobial bacterial cellulose, preparation method and application thereof - Google Patents
Antimicrobial bacterial cellulose, preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an antimicrobial bacterial cellulose, a preparation method and application thereof. The method includes the steps of: adding 1-10 parts by weight of bacterial cellulose and 0.5-10 parts by weight of a tetravalent cerium salt into 100-500 parts by weight of an acidic aqueous solution, in an inert environment, adding 10-100 parts by weight of an unsaturated quaternary ammonium salt monomer to carry out reaction at 30-80DEG C for 4-24h, then adding a polymerization inhibitor to terminate reaction, thus obtaining the antimicrobial bacterial cellulose. The method is very simple, is low in cost, and is beneficial to industrial production, also has no need of organic solvent, and can complete grafting reaction in an aqueous phase. The method provided by the invention has high grafting ratio, and can directly control the grafting ratio by controlling reaction temperature. The obtained antimicrobial bacterial cellulose has high stability, good antimicrobial effect and high biological safety.
Description
Technical field
The present invention relates to a kind of Antimicrobial bacterial cellulose and preparation method thereof and application, belong to biology medical material technical field.
Background technology
Bacteria cellulose (bacterial cellulose, be called for short BC) as a kind of novel " moist " dressing, it has unique physics, chemistry and mechanical properties, such as: ultra-fine reticulated structure, high-tensile and Young's modulus, high-hydrophilic, good ventilative water suction and water permeability, excellent retentiveness and high wet strength, good vivo and vitro biocompatibility, and the medical waste material produced after using can be degradable after cellulase treatment.Large quantity research shows that bacteria cellulose aquagel dressing can play the effect of heat and moisture preserving, effectively can promote wound healing simultaneously; And dressing can cut randomly, there is fabulous submissive property with skin, there is certain analgesic effect; Its ultra-fine reticulated structure, excellent mechanical property and tensile strength make auxiliary material have certain seamability, are convenient to fix.But bacteria cellulose itself does not possess anti-microbial property, and be in use easy to be subject to harmful microbe in air or water and pollute, thus cause a series of infection problems, therefore effectively to improve and to improve its antibacterial ability particularly important.Adopt bacteria cellulose to have unrivaled advantage such as other biomaterial, fabric etc. in the past as the base material of anti-biotic material, be expected to become a kind of comparatively ideal medical dressing.The simple bacteria cellulose of external employing has been reported as dressing, and industrialization is used for clinical, releases bacteria cellulose wound dressing and antibacterial wound dressing is also widely used clinically as Xylos company.And the domestic research about bacteria cellulose is still in the starting stage, about the research of bacteria cellulose dressing rarely has report.In sum, the stronger anti-microbial property giving bacteria cellulose is most important in the application of biomedical materials field to it.
Antibacterial function is possessed in order to make bacteria cellulose, the mode of prior art many employings physics compound, it adds anti-biotic material in the culturing process of bacteria cellulose, this mode makes the activity of bacteria cellulose synthesized micro-organism partly be suppressed, result in bacteria cellulose synthesis slowly, productive rate reduces greatly.Another kind of mode bacteria cellulose is placed in microbicide solution to obtain Antimicrobial bacterial cellulose by the mode of soaking absorption, but in this mode the adsorption efficiency of sterilant and stability not high, and the mode of adding antiseptic-germicide in the treatment in addition too increases the complicated property of operation.The method that CN101708341 B adopts bacteria cellulose aquagel and silver ion solution total immersion to steep has prepared carrying nano silver Antimicrobial bacterial cellulose hydrogel, although this material has good antimicrobial property, but nanometer silver is mainly deposited in bacteria cellulose network by the mode of physical adsorption, the release of nanometer silver more or less can be there is in its use procedure, and biological safety also exists dispute in academia in the body of nanometer silver always, current SFDA is comparatively careful to the reply of this type of medical material.CN101905031 B is equally also the method adopting physical adsorption antiseptic-germicide sulfonic acid pyrimidine silver, and its technology stability is difficult to ensure, thus its germ resistance can be subject to certain impact.Therefore, be no matter all efficient, simply can not must obtain Antimicrobial bacterial cellulose by the mode of physics compound or the mode of soaking absorption, and be difficult to ensure gained Antimicrobial bacterial cellulose stability, prevent antiseptic-germicide from entering human body.
CN103724569 A discloses a kind of Antimicrobial bacterial cellulose and preparation method thereof, this preparation method mainly comprises: first on bacteria cellulose main chain, introduce double bond containing unsaturated organic acid or acid anhydrides by esterification, and then the unsaturated double-bond introduced by esterification and unsaturated quaternary ammonium salt monomer polymerization reaction take place thus obtain Antimicrobial bacterial cellulose.Although can be obtained a kind of Antimicrobial bacterial cellulose of grafting by aforesaid method, the method more loaded down with trivial details, technique relative complex, is unfavorable for industrial production.Especially obtain the technique of the esterification bacteria cellulose containing double bond, the reaction of this step carries out under the molten reaction system of oil, the organic solvent that reaction needed is a large amount of, such as toluene, inevitably produce the pollution of organic solvent, biological safety is low, and improves the production cost of whole technique; In the program, the overall yield of grafting Antimicrobial bacterial cellulose and percentage of grafting are limited by esterification, as can be seen from this case Fig. 1, although before and after esterification there is certain difference in infared spectrum, but difference is not very large, illustrate that on bacteria cellulose, esterifying efficiency is not too high, therefore follow-up polyreaction percentage of grafting is lower and uncontrollable.
Therefore, how by simple, grafting success ratio is high and percentage of grafting is controlled, the simple synthetic method of aftertreatment prepares the active demand that stability is high, good anti-bacterial effect, biological safety are high Antimicrobial bacterial cellulose is this area.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of Antimicrobial bacterial cellulose, the method is better than prior art in the simplicity of technique, grafting success ratio, the controllability of percentage of grafting and the accessibility at least one aspect of aftertreatment.
Another object of the present invention is to provide a kind of Antimicrobial bacterial cellulose, this Antimicrobial bacterial cellulose is better than prior art in stability, antibacterial effect, biological safety at least one aspect.
Another object of the present invention is the application providing a kind of Antimicrobial bacterial cellulose.
For this reason, the invention provides a kind of preparation method of Antimicrobial bacterial cellulose on the one hand, described method comprises the steps: the tetravalent cerium salt of the bacteria cellulose of 1 ~ 10 weight part and 0.5 ~ 10 weight part to add in the acidic aqueous solution of 100 ~ 500 weight parts, in an inert atmosphere, add the unsaturated quaternary ammonium salt monomer of 10 ~ 100 weight parts, at 30 ~ 80 DEG C of reaction 4 ~ 24h, add stopper termination reaction, obtain described Antimicrobial bacterial cellulose.
In the preparation method of Antimicrobial bacterial cellulose of the present invention, preferably, described tetravalent cerium salt is 1 ~ 5 weight part.
In the preparation method of Antimicrobial bacterial cellulose of the present invention, preferably, described acidic aqueous solution is 200 ~ 400 weight parts.
In the preparation method of Antimicrobial bacterial cellulose of the present invention, preferably, described unsaturated quaternary ammonium salt monomer is 30 ~ 80 weight parts.
In the preparation method of Antimicrobial bacterial cellulose of the present invention, preferably, described temperature of reaction is 40 ~ 75 DEG C; More preferably, described temperature of reaction is 50 ~ 75 DEG C; Again preferably, described temperature of reaction is 60 ~ 75 DEG C.
The present invention with quadrivalent cerium ion for initiator, direct grafting unsaturated quaternary ammonium salt class monomer on bacteria cellulose main chain, compared to the method for the first esterification post polymerization that CN103724569 A provides, method of the present invention is very simple, cost is low, is conducive to industrial production; And without the need to an organic solvent, can graft reaction be completed in sour water phase system; Method percentage of grafting of the present invention is high, and directly can control percentage of grafting by controlling temperature of reaction.
According to specific embodiment of the invention scheme, in the preparation method of Antimicrobial bacterial cellulose of the present invention, also comprise and the described Antimicrobial bacterial cellulose obtained is boiled 10 ~ 120min in boiling water, preferably 30 ~ 90min.Optionally carry out purification process afterwards, such as washing, dry or moist, sterilizing.Wherein, drying means can adopt ordinary method of the prior art, such as seasoning, centrifugal drying, vacuum-drying, machinery pressure are except one or more in the methods such as drying, lyophilize, dry degree can be determined according to the state of required Antimicrobial bacterial cellulose, and the state of required Antimicrobial bacterial cellulose can be selected according to different wound type; Such as, for dry wound, need moist dressing be adopted, then can choice for use Antimicrobial bacterial cellulose hydrogel, now, above-mentioned drying means maybe can be adopted to remove portion of water without the need to drying; And for there being the wound of a large amount of transudate, then select the germ resistance bacteria cellulose of dry state, now, dewater substantially completely by above-mentioned drying means.Sterilising method can adopt ordinary method of the prior art, such as, adopts the methods such as gamma-radiation, pressure steam or high-energy electron irradiation to carry out sterilizing after the Antimicrobial bacterial cellulose obtained can being packed.
According to specific embodiment of the invention scheme, in the preparation method of Antimicrobial bacterial cellulose of the present invention, wherein, described unsaturated quaternary ammonium salt monomer is the quaternary ammonium salt containing unsaturated link(age).Preferably, described unsaturated quaternary ammonium salt monomer includes but not limited to one or more in methylacryoyloxyethyl trimethyl-ammonium halide, acrylyl oxy-ethyl-trimethyl ammonium halide, acryloyl-oxyethyl dimethyl benzyl ammonium halide, such as MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride, acrylyl oxy-ethyl-trimethyl salmiac, acryloxyethyldimethyl benzyl ammonium chloride, methylacryoyloxyethyl trimethylammonium bromide, acrylyl oxy-ethyl-trimethyl brometo de amonio, acryloxyethyldimethyl Benzylphosphonium Bromide ammonium etc.Preferably, the ultimate density after described unsaturated quaternary ammonium salt monomer adds reaction system is 0.1 ~ 2.0mol/L, and more preferably, its ultimate density is 0.5 ~ 1.5mol/L.
According to specific embodiment of the invention scheme, in the preparation method of Antimicrobial bacterial cellulose of the present invention, wherein, the cerium salt of described tetravalent cerium salt to be the valence state of cerium be tetravalence, includes but not limited to ceric ammonium nitrate.
According to specific embodiment of the invention scheme, in the preparation method of Antimicrobial bacterial cellulose of the present invention, wherein, described acidic aqueous solution includes but not limited to one or more in aqueous nitric acid, aqueous sulfuric acid, aqueous hydrochloric acid, high chloro acid solution.Preferably, the concentration of described acidic aqueous solution is 1.0 × 10
-2~ 1.0mol/L, more preferably, its concentration is 0.05 ~ 0.5mol/L.
According to specific embodiment of the invention scheme, in the preparation method of Antimicrobial bacterial cellulose of the present invention, wherein, described stopper includes but not limited to Resorcinol, 2-Tert. Butyl Hydroquinone or 2, one or more in 5-di-tert-butyl hydroquinone, its consumption is 50% ~ 100% of described bacteria cellulose quality.Preferably, described stopper can be mixed with mass concentration be 0.5% ~ 5% the stopper aqueous solution be added in reaction system.
Bacteria cellulose described in the present invention is the Mierocrystalline cellulose of Microbe synthesis, the polymerization degree of usually described bacteria cellulose is 1000 ~ 5000, it can be bought (such as, in Hainan hundred million moral Food Co., Ltd) or by prior art in the method recorded prepare, such as can prepare as follows:
Bacteria cellulose being produced bacterial strain is inoculated in described nutrient solution in culture volume than the ratio of 1:100, and then under 28 DEG C ~ 32 DEG C cleaning conditions, static cultivation obtains bacteria cellulose film in 3 ~ 7 days.Nutrient solution is wherein: 0.1 ~ 0.4g/ml glucose, 0.03 ~ 0.06g/ml peptone, 0.02 ~ 0.03g/ml yeast powder, 0.01 ~ 0.02g/ml Sodium phosphate dibasic, 0.005 ~ 0.015g/ml magnesium sulfate, 0.005 ~ 0.01g/ml ammonium sulfate, 0.005 ~ 0.015ml/ml maize treacle extracting solution.
Wherein said bacteria cellulose is produced bacterial strain and is included but not limited to acetobacter xylinum, produces acetobacter, acetify bacillus, Acetobacter pasteurianus, glucose bacillus, Agrobacterium, root nodule bacterium, sarcina, pseudomonas cepacia, Pseudomonas cocovenenans or campylobacter jejuni.
According to specific embodiment of the invention scheme, in the preparation method of Antimicrobial bacterial cellulose of the present invention, wherein said bacteria cellulose is the bacteria cellulose of purifying, the bacteria cellulose of purifying can be bought or prepare by prior art, such as, method in CN103724569A, or prepare as follows:
The a large amount of clear water of bacteria cellulose film crude product obtained after cultivation is repeatedly rinsed substratum and the residual body of bacterium on removing surface; Be the sodium lauryl sulphate (SDS) of 1% ~ 3% again by mass concentration, under 60 DEG C of conditions, stir immersion 12 ~ 24h, to remove the residual foreign protein inside bacteria cellulose; After clean with a large amount of deionized water rinsing, by 0.1 ~ 1.0mol/L NaOH solution, process 1 ~ 3h under 60 DEG C of conditions, removed pyrogen in bacteria cellulose; Also use repeatedly distilled water immersion to neutral by the acetic acid solution neutralizing treatment of 0.1mol/L again, precooling 4 ~ 24h in-20 ~ 80 DEG C of refrigerators, carries out lyophilize 24 ~ 48h in freeze drier, obtain dried BC dry film, and drying at room temperature saves backup.
On the other hand, the invention provides a kind of Antimicrobial bacterial cellulose, it take bacteria cellulose as main chain, obtained by grafting unsaturated quaternary ammonium salt, and the percentage of grafting of described Antimicrobial bacterial cellulose is 5% ~ 40%, preferably, percentage of grafting is 9% ~ 30%, more preferably, percentage of grafting is 15% ~ 30%.Described Antimicrobial bacterial cellulose can prepare according to method of the present invention.Because the present invention adopts graft reaction to be grafted on bacteria cellulose chain by quaternary ammonium salt unit by covalent linkage, therefore Antimicrobial bacterial cellulose of the present invention is stable high, can effectively prevent antiseptic-germicide from entering human body.The present invention confirms that described Antimicrobial bacterial cellulose has good antibacterial effect to intestinal bacteria, streptococcus aureus etc. by experiment, and along with the raising of percentage of grafting, antibacterial effect is better.Owing to not using any organic solvent in preparation method of the present invention, therefore, the Antimicrobial bacterial cellulose biological safety of gained of the present invention is high.
Again on the one hand, the invention provides described Antimicrobial bacterial cellulose and preparing the application in antiseptic dressing, preferably, described antiseptic dressing is Chinese People's Anti-Japanese Military and Political College enterobacteria and/or staphylococcus glucose coccus dressing.Because described Antimicrobial bacterial cellulose of the present invention has satisfactory stability, antibacterial effect and biological safety, therefore, when Antimicrobial bacterial cellulose of the present invention is used as the dressing promoting wound healing, can effective prevent wound infection.
In sum, the invention provides a kind of Antimicrobial bacterial cellulose and preparation method thereof, described method is very simple, and cost is low, is conducive to industrial production; And without the need to an organic solvent, can graft reaction be completed in aqueous phase system; Method percentage of grafting of the present invention is high, and directly can control percentage of grafting by controlling temperature of reaction.The Antimicrobial bacterial cellulose obtained stablizes height, good anti-bacterial effect, biological safety are high.
Accompanying drawing explanation
Fig. 1 is the infared spectrum of raw material BC and grafting BC I.
Fig. 2 is raw material BC, grafting BC I, grafting BC II and grafting BC III Chinese People's Anti-Japanese Military and Political College enterobacteria design sketch.
Fig. 3 is raw material BC, grafting BC I, grafting BC II and grafting BC III anti-Staphylococcus aureus design sketch.
Embodiment
In order to there be understanding clearly to technical characteristic of the present invention, object and beneficial effect, now in conjunction with specific examples, following detailed description is carried out to technical scheme of the present invention, these examples should be understood and be only not used in for illustration of the present invention and limit the scope of the invention.
Embodiment 1
The present embodiment prepares used bacteria cellulose as follows:
Bacteria cellulose being produced bacterial strain (ATCC700178) is inoculated in nutrient solution in culture volume than the ratio of 1:100, and then under 30 DEG C of cleaning conditions, static cultivation obtains bacteria cellulose film in 7 days.Nutrient solution is wherein: 20.0g/L glucose, 5.0g/L peptone, 5.0g/L yeast powder, 2.7g/L Sodium phosphate dibasic, 1.0g/ml magnesium sulfate, 1.0g/ml ammonium sulfate, 1.0ml/ml maize treacle extracting solution.
The bacteria cellulose film crude product of above-mentioned acquisition is repeatedly rinsed substratum and the residual body of bacterium on removing surface with a large amount of clear water; Be the sodium lauryl sulphate (SDS) of 2.0% again by mass concentration, stir under 60 DEG C of conditions and soak 24h, to remove the residual foreign protein inside bacteria cellulose; After clean with a large amount of deionized water rinsing, use 1.0mol/LNaOH solution, under 60 DEG C of conditions, process 2h, to remove pyrogen in bacteria cellulose; Also use repeatedly distilled water immersion to neutral by the acetic acid solution neutralizing treatment of 0.1mol/L again, precooling 24h in-80 DEG C of refrigerators, carries out lyophilize 24h in freeze drier, obtains dried BC dry film, as shown in Figure 1, and drying at room temperature saves backup its infared spectrum.
Take dried BC dry film and the 0.55g ceric ammonium nitrate of 0.5g 3cm × 3cm, successively join containing 100ml 8 × 10
-2in the round bottom there-necked flask of the aqueous nitric acid of mol/L, be placed in the water-bath of 70 DEG C, magnetic agitation, and after slowly passing into nitrogen 30min, add MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (METAC) aqueous solution of 10.4g, continuing to pass into nitrogen, is 70 DEG C of reaction 12h in temperature of reaction.The Resorcinol aqueous solution termination reaction that 30ml mass concentration is 1.0% is added after question response terminates, take out the BC after grafting to be placed in 100 DEG C of boiling water and to boil after 60min carries out purification process, obtain Antimicrobial bacterial cellulose hydrogel, be designated as grafting BC I, as shown in Figure 1, the collection of illustrative plates contrasting raw material BC and the grafting BC I used can find out that grafting BC I is at about 1728cm to its infared spectrum
-1there is new absorption peak in place, it is the stretching vibration peak of ester group in the METAC of grafting, at about 1480cm
-1there is the charateristic avsorption band of methyl c h bond on quaternary ammonium group in place, this illustrates that METAC success graft polymerization is to BC surface.
Embodiment 2 ~ 7
In order to inquire into the impact of temperature of reaction on percentage of grafting, embodiment 2 ~ 7 only changes the bath temperature in embodiment 1, makes this reaction be 30 DEG C, 40 DEG C, 50 DEG C, 60 DEG C, 65 DEG C, 80 DEG C in temperature of reaction respectively and carries out.Observe in experimentation, when temperature of reaction is 80 DEG C, BC is cracked into little fragment, destroy the globality of material, therefore carry out graft polymerization with this understanding and there is no great practical application meaning, grafting BC can be obtained under remaining reaction temperature condition, wherein, be that 60 DEG C, 65 DEG C gained grafting BC are designated as BC II, BC III respectively by temperature of reaction.
Utilize German Vario EL meta analysis instrument to test the content of nitrogen element in sample to each grafting BC obtained in raw material BC and embodiment 1 ~ 6, be designated as N%, because BC itself is not containing nitrogen element, therefore according to formula (1) (2):
G1％＝N％×M(METAC)/M(N) (1)
G％＝G1/(100-G1)×100％ (2)
Record percentage of grafting, its result is as shown in table 1:
Table 1
| Temperature of reaction/DEG C | 30 | 40 | 50 | 60 | 65 | 70 |
| N content/% | 0.14 | 0.21 | 0.34 | 0.595 | 0.910 | 1.525 |
| Percentage of grafting G/% | 2.1 | 3.2 | 5.31 | 9.68 | 15.61 | 29.24 |
As can be seen from Table 1, when graft reaction temperature is lower, the percentage of grafting of BC is very low, but along with the rising of graft reaction temperature, the percentage of grafting of bacteria cellulose also improves thereupon, be 70 DEG C in temperature of reaction, the percentage of grafting of bacteria cellulose can reach 29.2%, and namely the present invention can control the percentage of grafting of controlling reaction temperature bacteria cellulose easily.
Embodiment 8
Raw material BC, grafting BC I, grafting BC II and grafting BC III is tested respectively to the antibacterial effect of intestinal bacteria and streptococcus aureus with reference to GB/T 20944.2-2007, its result respectively as shown in Figure 2 and Figure 3, the antibacterial effect of grafting BC I of the present invention, grafting BC II and grafting BC III is all better than raw material BC as can be seen from Figure 2, and along with the raising of percentage of grafting, anticolibacillary effect is better; The antibacterial effect of grafting BC I of the present invention, grafting BC II and grafting BC III is all better than raw material BC as can be seen from Figure 3, and along with the raising of percentage of grafting, the effect of anti-Staphylococcus aureus is better.
Embodiment 9
To buy after the bacteria cellulose deionized water rinsing of Hainan hundred million moral Food Co., Ltd, be the sodium lauryl sulphate (SDS) of 1.0% again by mass concentration, stir under 60 DEG C of conditions and soak 24h, to remove the residual foreign protein inside bacteria cellulose; After clean with a large amount of deionized water rinsing, use 0.1mol/L NaOH solution, under 60 DEG C of conditions, process 3h, pyrogen in removing bacteria cellulose; Also use repeatedly distilled water immersion to neutral by the acetic acid solution neutralizing treatment of 0.1mol/L again, precooling 12h in-80 DEG C of refrigerators, carries out lyophilize 24h in freeze drier, obtain dried BC dry film, and drying at room temperature saves backup.
Take dried BC dry film and the 1.65g ceric ammonium nitrate of 1.0g 3cm × 3cm, successively join containing 300ml 10 × 10
-2in the round bottom there-necked flask of the aqueous nitric acid of mol/L, be placed in the water-bath of 60 DEG C, magnetic agitation, and after slowly passing into nitrogen 30min, add MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (METAC) aqueous solution of 10.0g, continuing to pass into nitrogen, is 60 DEG C of reaction 12h in temperature of reaction.Add the Resorcinol aqueous solution termination reaction that 70ml mass concentration is 1.0% after question response terminates, take out the BC after grafting and be placed in 100 DEG C of boiling water and boil after 60min carries out purification process, obtain Antimicrobial bacterial cellulose hydrogel.The percentage of grafting being obtained this sample by the cubage of German Vario EL elemental analyser test sample nitrogen element is 10.57%.
Embodiment 10
To buy after the bacteria cellulose deionized water rinsing of Hainan hundred million moral Food Co., Ltd, be the sodium lauryl sulphate (SDS) of 3.0% again by mass concentration, stir under 60 DEG C of conditions and soak 12h, to remove the residual foreign protein inside bacteria cellulose; After clean with a large amount of deionized water rinsing, use 1.0mol/L NaOH solution, under 60 DEG C of conditions, process 2h, pyrogen in removing bacteria cellulose; Also use repeatedly distilled water immersion to neutral by the acetic acid solution neutralizing treatment of 0.1mol/L again, precooling 12h in-80 DEG C of refrigerators, carries out lyophilize 24h in freeze drier, obtain dried BC dry film, and drying at room temperature saves backup.
Take dried BC dry film and the 1.65g ceric ammonium nitrate of 2.0g 3cm × 3cm, successively join containing 400ml 10 × 10
-2in the round bottom there-necked flask of the aqueous nitric acid of mol/L, be placed in the water-bath of 75 DEG C, magnetic agitation, and after slowly passing into nitrogen 30min, add MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride (METAC) aqueous solution of 50.0g, continuing to pass into nitrogen, is 75 DEG C of reaction 12h in temperature of reaction.Add the Resorcinol aqueous solution termination reaction that 100ml mass concentration is 1.0% after question response terminates, take out the BC after grafting and be placed in 100 DEG C of boiling water and boil after 60min carries out purification process, obtain Antimicrobial bacterial cellulose hydrogel.The percentage of grafting being obtained this sample by the cubage of German Vario EL elemental analyser test sample nitrogen element is 32.79%.
Claims (10)
1. the preparation method of an Antimicrobial bacterial cellulose, described method comprises the steps: the tetravalent cerium salt of the bacteria cellulose of 1 ~ 10 weight part and 0.5 ~ 10 weight part to add in the acidic aqueous solution of 100 ~ 500 weight parts, in an inert atmosphere, add the unsaturated quaternary ammonium salt monomer of 10 ~ 100 weight parts, at 30 ~ 80 DEG C of reaction 4 ~ 24h, add stopper termination reaction, namely obtain described Antimicrobial bacterial cellulose.
2. method according to claim 1, wherein, after described method also comprises and obtains described Antimicrobial bacterial cellulose, boils 10 ~ 120min by this Antimicrobial bacterial cellulose, preferably 30 ~ 90min in boiling water.
3. method according to claim 1, wherein, described unsaturated quaternary ammonium salt monomer comprises one or more in methylacryoyloxyethyl trimethyl-ammonium halide, acrylyl oxy-ethyl-trimethyl ammonium halide, acryloyl-oxyethyl dimethyl benzyl ammonium halide; Preferably, the ultimate density after described unsaturated quaternary ammonium salt monomer adds reaction system is 0.1 ~ 2.0mol/L.
4. method according to claim 1, wherein, described tetravalent cerium salt is ceric ammonium nitrate.
5. method according to claim 1, wherein, described acidic aqueous solution comprises one or more in aqueous nitric acid, aqueous sulfuric acid, aqueous hydrochloric acid, high chloro acid solution; Preferably, the concentration of described acidic aqueous solution is 1.0 × 10
-2~ 1.0mol/L.
6. method according to claim 1, wherein, described stopper comprises one or more in Resorcinol, 2-Tert. Butyl Hydroquinone, 2,5 di tert butyl hydroquinone, and its consumption is 50% ~ 100% of described bacterial fibers quality; Preferably, described stopper can be mixed with mass concentration be 0.5% ~ 5% the stopper aqueous solution be added in reaction system.
7. method according to claim 1, wherein, described bacteria cellulose is the bacteria cellulose of purifying.
8. an Antimicrobial bacterial cellulose, it take bacteria cellulose as main chain, obtained by grafting unsaturated quaternary ammonium salt, and the percentage of grafting of described Antimicrobial bacterial cellulose is 5% ~ 40%, preferably, percentage of grafting is 9% ~ 30%, more preferably, percentage of grafting is 15% ~ 30%.
9. Antimicrobial bacterial cellulose according to claim 8, it is that method according to any one of claim 1 ~ 7 prepares.
10. the Antimicrobial bacterial cellulose prepared in claim 1 ~ 7 or the Antimicrobial bacterial cellulose described in claim 8 ~ 9 are preparing the application in antiseptic dressing, preferably, described antiseptic dressing is the dressing of Chinese People's Anti-Japanese Military and Political College enterobacteria and/or staphylococcus glucose coccus.
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| CN105284812A (en) * | 2015-11-26 | 2016-02-03 | 郑州欧姆康生物材料有限公司 | Broad-spectrum antibacterial amphiphilic biological carbon material, and preparation method and application thereof |
| CN109749137A (en) * | 2018-12-17 | 2019-05-14 | 苏州艾美医疗用品有限公司 | A kind of preparation method of aquagel dressing |
| CN110038151A (en) * | 2019-05-16 | 2019-07-23 | 中原工学院 | A kind of preparation method of bacteria cellulose-base long acting antibiotic wound dressing |
| CN110801529A (en) * | 2019-10-31 | 2020-02-18 | 西安交通大学 | Modified bacterial cellulose/heparin/gelatin medical dressing and preparation method thereof |
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