CN1559433A - Polyhexose type nanometer antimicrobial matter, prepn. method and use thereof - Google Patents
Polyhexose type nanometer antimicrobial matter, prepn. method and use thereof Download PDFInfo
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- CN1559433A CN1559433A CNA2004100164402A CN200410016440A CN1559433A CN 1559433 A CN1559433 A CN 1559433A CN A2004100164402 A CNA2004100164402 A CN A2004100164402A CN 200410016440 A CN200410016440 A CN 200410016440A CN 1559433 A CN1559433 A CN 1559433A
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Abstract
A polyose-type nano-class antibacterial material used for medicines or as the additive of feed is prepared from chitosan and bactericiding metal ions.
Description
Technical field
The present invention relates to a kind of is basic material with the chitosan, has the polysaccharide nano anti-biotic material and its production and use of the metal ion of bactericidal activity by load.
Background technology
Chitosan is natural high-molecular biologic oligomer, and its catabolite is for having weakly alkaline glucosamine, and is nontoxic, harmless to tissue.It also has the unique biological activity except that having excellent biocompatibility, can regulate the animal body immunity, suppresses tumor cell proliferation, stronger bacteriostatic activity is arranged, and can regulate animal body inner cholesterol and lipid metabolism.Chitosan has been applied to agricultural, industry and medicine and other fields as multiple functional materials such as feed additive, heavy metal chelant, adsorbent, medicinal slow release agents.Multiple chitin modified product is also better used as cross-linked chitosan, chitosan microball, chitin nanometer etc.Chitosan microball, pearl chitosan have been studied and have been applied to cancer therapy drug and proteinic controlled release system.The method for preparing the pearl chitosan has water oil two phase process, emulsion droplet technology, spray drying method etc., and these preparation process are complicated and need with an organic solvent and surfactant usually, and Zhi Bei chitosan microball is not suitable for physico-chemical property and characterizes observation thus.
Zhengrong Cui; Russell J Mumper.Chitosan-based nanoparticles fortopical genetic immunization.Journal of Controlled Release.2001,75 (3): the 409-419 report, cohesion in acid solution makes CS (chitosan)-DNA nanoparticle by CS and DNA, the particle diameter of CS-DNA nanoparticle is between 100-250nm, and synthetic CS-DNA nanoparticle can be applied to the mice genetic immunization.
Yong Hu; Xiqun Jiang, Yin Ding, et.al.Synthesis and characterizationof chitosan-poly (acrylic acid) nanoparticles.Biomaterials, 2002, the 23:3193-3201 report, prepare CS-PAA (poly acrylic acid) nanoparticle by acrylic acid matrix polymerization effect in chitosan solution, can stable dispersion in acid medium.But above prepared nano particle diameter is bigger usually, and yield rate is lower, and the diameter of particle heterogeneity that forms.
Nano material is applied in the commercial production as anti-biotic material.Nano material with antibacterial functions, according to the difference of sterilization mechanism, can be divided into two classes: a class is for being loaded with Ag
+Nano material, utilize Ag
+Can make the albumen inactivation on the cell membrane, thus cell killing; Another kind of for being loaded with ZnO or TiO
2Etc. the nano material of material, they can produce conduction band electron and valence band hole, and the latter are good oxidants, has very strong reactivity under illumination condition, can with the H of surface adsorption
2O or OH
-Ion reacts and forms the hydroxyl with strong oxidizing property, thereby by the strong oxidizing property of hydroxyl and cell killing, and penetrable cell membrane, destroy membrane structure, toxin " the Xiong Dexin that degradation of cell produces, Liang Ming, Cui Dejian. nano material is to the mensuration of common aerobic pathogenic bacterium minimum inhibitory concentration. the clinical new medical science of China.2002，3(10)：879-880》。The ultrafine metal particle such as Ag, Cu, Zn that will have sterilization, an antibacterial activity with ion exchange in the porous zeolite microparticles is adsorbed in the hole, add then in the fiber, make the fiber product that escherichia coli, staphylococcus, various mycete and water worm etc. is had sterilization, antibiotic property.But the acid resistance of the sub-crystal structure of porous zeolite microparticles is poor, and therefore, under acid condition, the ion exchange condition of Ag, Cu, Zn and the repeatability of adsorption effect are difficult.Japan has developed the TiO with anti-microbial property in nineteen ninety
2Small porous particle makes solid nano TiO to replace traditional zeolite
2Be applied to sterilization material " Liu Jingchun, the Huanghai Sea, Zuo Meixiang etc. the nano silver-supported antibacterial material with promote healthy. material Leader .2000,10 (14): 300-301 ".
Chitosan is the same with other polysaccharide, contains highly active functional group in its complicated spatial structure, shows the antibiotic feature of class, and the growth that can suppress various bacteria is with active.Has the degradable chitosan of biocompatibility because its antibacterial activity is manifesting very big prospect aspect the antibiotic organic nano material of preparation.
Summary of the invention
The purpose of this invention is to provide a kind of polysaccharide nano anti-biotic material that antibiotic, antiviral drugs or feed additive use and preparation method thereof that can be used as.
Polysaccharide nano anti-biotic material of the present invention is the carrying metal ion chitin nanometer, particle diameter 20-500nm, and wherein the molecular weight of chitosan is 2～80kDa, and deacetylation is 50～100%, and the metal ion weight content is 1～30%.
The preparation method of polysaccharide nano anti-biotic material of the present invention has two kinds of schemes.
Scheme 1, preparation process is as follows:
Under 20-60 ℃ of stirring, adding molecular weight in dilute acid soln is 2～80kDa, deacetylation is 50～100% chitosans, and configuration 0.1%～5% chitosan acid solution adds 0.1～5% cross-linking agent solution to the chitosan acid solution then, in the course of reaction, adding concentration simultaneously is 100～1000mg/L metal ion solution, after reacting completely, and centrifugalize, the precipitate distilled water wash is to neutral, and lyophilization promptly gets the polysaccharide nano anti-biotic material.
Under 20-60 ℃ of stirring, adding molecular weight in dilute acid soln is 2～80kDa, deacetylation is 50～100% chitosans, configuration 0.1%～5% chitosan acid solution, add 0.1～5% cross-linking agent solution to the chitosan acid solution then, form microemulsion, centrifugalize, the rinsing of precipitate distilled water is to neutral, lyophilization gets chitin nanometer, and chitin nanometer dry powder being placed concentration again is 100～1000mg/L metal ion solution, vibration absorption, chitin nanometer after the absorption is placed oven for drying, promptly get the polysaccharide nano anti-biotic material.
Among the present invention, said diluted acid is acetic acid, acetic acid or hydrochloric acid; Cross-linking agent is the anion cross-linking agent, comprises sodium polyphosphate, sodium sulfate or sodium citrate etc.; Metal ion solution is sulfate, hydrochlorate, the nitrate aqueous solution of copper ion, zinc ion or is the nitrate aqueous solution of silver ion.
Advantage of the present invention:
1) the invention provides a kind of in (being under the temperate condition) preparation polysaccharide nano anti-biotic material method under room temperature, the normal pressure.In the preparation process, do not use any organic reagent and surfactant, well solved the separation and the issues of purification of chitosan nanoparticles.
2) evenly (particle diameter is about 20～500nm) to the nano particle diameter of polysaccharide nano anti-biotic material gained under identical preparation condition of making of the present invention size, and form is good.
3) the present invention is a substrate with metal ion and the chitosan with bactericidal activity, prepare nanoparticle by introducing the multivalent anions cross-linking agent, it can be widely used in animal husbandry or be applied to field of medicaments as antibacterials as antibiotic, antiviral drugs or feed additive.
Description of drawings
Fig. 1 is prepared into polysaccharide nano anti-biotic material perspective Electronic Speculum figure for example 1, and particle diameter is about 30nm, 50000 times of amplifications;
Fig. 2 is example 2 preparation gained polysaccharide nano anti-biotic material atomic force microscope figure, and particle diameter is about 60nm, and wherein, figure is a nano anti-biotic material atomic force microscope plane graph a), figure b) be its axonometric chart;
Fig. 3 is example 3 preparation gained polysaccharide nano anti-biotic material low power sem photographs (2000 times of amplifications), and particle diameter is about 70nm;
Fig. 4 is example 4 preparation gained polysaccharide nano anti-biotic material atomic force microscope figure, and particle diameter is about 60nm; Wherein, figure is a nano anti-biotic material atomic force microscope plane graph a), figure b) be its axonometric chart;
Fig. 5 is example 4 preparation gained polysaccharide nano anti-biotic material particle size distribution figure;
Fig. 6 is example 5 preparation gained polysaccharide nano anti-biotic material atomic force microscope figure, and particle diameter is about 50nm, and figure is a nano anti-biotic material atomic force microscope plane graph a), figure b) be its axonometric chart;
Fig. 7 is example 5 preparation gained polysaccharide nano anti-biotic material particle size distribution figure;
Fig. 8 is example 6 preparation gained chitin nanometer atomic force microscope figure, and wherein, figure is a nano anti-biotic material atomic force microscope plane graph a), figure b) be its axonometric chart; Nanoparticle is than the regular spherical structure, and is more regular flakes coherent condition, and particle diameter is about 40nm;
Fig. 9 be example 8 polysaccharide nano anti-biotic material drug sensitive experiments to Salmonella bactericidal action atomic force microscope figure, wherein, figure a) is a Salmonella somatic cells aspect graph after the nano anti-biotic material effect, figure b) be its axonometric chart; Salmonella can be observed salmonella cell body content and rush down outward behind polysaccharide nano anti-biotic material effect 3h, residual cell appearance profile only, and nanoparticle enters in the Salmonella thalline by the cell wall cavity.
The specific embodiment
Further specify the present invention below in conjunction with instantiation.
Example 1:
Under 20 ℃ of magnetic agitation, the chitosan that in 0.5% acetic acid solution, adds molecular weight 9kDa, deacetylation 85%, dispose 0.1% chitosan acid solution, add 0.1% polyphosphoric acids sodium solution in the chitosan acetic acid solution, in the course of reaction, adding copper ion concentration is the 100mg/L copper-bath, after reacting completely, 3000rpm/min is centrifugal, and the rinsing of precipitate distilled water is to neutrality, and lyophilization promptly gets the polysaccharide nano anti-biotic material.
The copper-loaded nanoparticle mean diameter of method for preparing is about 30nm, and wherein copper content is about 1%, and perspective Electronic Speculum figure shows that nanoparticle is than regular spherical structure (see figure 1), can stablize preservation in pH value 3～8.
Example 2:
Under 60 ℃ of magnetic agitation, the chitosan that in 0.5 acetum, adds molecular weight 10kDa, deacetylation 84%, dispose 5% chitosan acid solution, add 5% metabisulfite solution in the chitosan acetic acid solution, in the course of reaction, adding zinc ion concentration is the 1000mg/L liquor zinci chloridi, after reacting completely, 9000rpm/min is centrifugal, and the rinsing of precipitate distilled water is to neutrality, and lyophilization promptly gets the polysaccharide nano anti-biotic material.
The zinc nanoparticle mean diameter of carrying of method for preparing is about 60nm, and wherein zinc content is about 30%, and atomic force microscope figure shows that nanoparticle is than regular spherical structure (see figure 2), can stablize preservation in pH value 3～8.
Example 3:
Under 30 ℃ of magnetic agitation, the chitosan that in 1% hydrochloric acid solution, adds molecular weight 8kDa, deacetylation 86%, dispose 2% chitosan acid solution, add 1% sodium citrate solution in the chitosan acetic acid solution, in the course of reaction, adding copper ion concentration is the 800mg/L copper nitrate solution, after reacting completely, 6000rpm/min is centrifugal, and the rinsing of precipitate distilled water is to neutrality, and lyophilization promptly gets the polysaccharide nano anti-biotic material.
The copper-loaded nanoparticle mean diameter of method for preparing is about 70nm, and wherein copper content is about 10%, and low power Scanning Electron Microscope photos reveal nanoparticle is irregular strumae structure (see figure 3), can stablize preservation in pH value 3～8.
Example 4:
Under 35 ℃ of magnetic agitation, the chitosan that in 1% acetic acid solution, adds molecular weight 9kDa, deacetylation 100%, dispose 1.5% chitosan acid solution, adding copper ion concentration in the chitosan acetic acid solution is the 400mg/L copper-bath, in the course of reaction, adds 0.5% sodium citrate solution simultaneously, after reacting completely, 3000rpm/min is centrifugal, and the rinsing of precipitate distilled water is to neutrality, and lyophilization promptly gets the polysaccharide nano anti-biotic material.
The polysaccharide nano anti-biotic material mean diameter of method for preparing is about 60nm, and wherein copper content is about 20%, and atomic force microscope figure shows that nanoparticle is that its particle size distribution is seen Fig. 5 than regular spherical structure (see figure 4), can stablize preservation in pH value 3～8.
Example 5:
Under 25 ℃ of magnetic agitation, in 0.5% acetic acid solution, add molecular weight 8kDa, the chitosan of deacetylation 50%, dispose 1% chitosan acid solution, in the chitosan acetic acid solution, add 0.5% sodium citrate solution, form microemulsion, the 4000rpm/min centrifugalize, the rinsing of precipitate distilled water is to neutral, lyophilization gets chitin nanometer, chitin nanometer dry powder is placed 600mg/L zinc ion solution, and the 300rpm/min absorption of vibrating is after the absorption fully, to adsorb the back chitin nanometer and place 60 ℃ of oven dry of baking oven, promptly get the polysaccharide nano anti-biotic material.
The polysaccharide nano anti-biotic material mean diameter of method for preparing is about 50nm, wherein zinc content is about 20%, and atomic force microscope shows that the polysaccharide nano anti-biotic material is that its particle size distribution is seen Fig. 7 than regular spherical structure (see figure 6),, can in pH value 3～8, stablize preservation.
Example 6:
Under 30 ℃ of magnetic agitation, in 0.5% acetic acid solution, add molecular weight 80kDa, the chitosan of deacetylation 84%, dispose 2% chitosan acid solution, in the chitosan acetic acid solution, add 1% sodium citrate solution, form microemulsion, the 6000rpm/min centrifugalize, the rinsing of precipitate distilled water is to neutral, lyophilization gets chitin nanometer, chitin nanometer dry powder is placed the 800mg/L copper ion solution, and the 400rpm/min absorption of vibrating is after the absorption fully, to adsorb the back chitin nanometer and place 60 ℃ of oven dry of baking oven, promptly get the polysaccharide nano anti-biotic material.
The polysaccharide nano anti-biotic material mean diameter of method for preparing is about 40nm, wherein copper content is about 10%, atomic force microscope figure shows that chitin nanometer is than the regular spherical structure, and be more regular flakes coherent condition, polysaccharide nano anti-biotic material atomic force microscope figure shows the better spherical structure (see figure 8) of form, can stablize preservation in pH value 3～8.
Example 7:
The piglet diarrhea that the polysaccharide nano anti-biotic material of application the present invention preparation is caused by coli-infection as antibacterial drug therapy.With 28 age in days ablactational baby pig is experimental subject, be that test material is established two test group with polysaccharide nano anti-biotic material, antibiotic respectively, test group is divided into interpolation respectively, is not added two groupings of coli strain, each test group is established three Concentraton gradient (setting of Concentraton gradient is with reference to the result of bacteriostatic experiment), each Concentraton gradient is established three repetitions, and other establishes a matched group (basal diet of feeding).Meter record every day feed intake is calculated daily gain and diarrhea rate.Raise when finishing, calculate each test group mortality rate respectively, and escherichia coli quantity influences intestinal microbial population with evaluation polysaccharide nano anti-biotic material in the detection duodenum content.
Table 1 has provided polysaccharide nano anti-biotic material treatment piglet diarrhea experiment effect.
Experimental result shows that the polysaccharide nano anti-biotic material can effectively be treated because the piglet diarrhea that coli-infection causes reduces intestinal contents escherichia coli quantity, reduces the piglet mortality rate, strengthens pigling immunity.
Example 8:
Polysaccharide nano anti-biotic material drug sensitive experiment.With tested bacteria incubated overnight on sterilization Mueller-Hinton (MH) bouillon agar flat board, picking colony be inoculated in MH in the sterilization test tube in, 37 ℃, 180rpm/min incubated overnight.Bacterium liquid after cultivating is diluted to 2-7 * 10
5CFU/ml first respectively adds the bacterium liquid of 100 microlitres to 11-holes in 96 aseptic hole flat boards, the 12 hole does not add bacterium liquid and adds 100 microlitre MH meat soups.Add corresponding antimicrobial one by one from ten holes, first hole to the then, 11-holes does not add antibacterial as the scanning control wells, 37 ℃, 90rpm/min were cultivated 18-24 hour, and the final concentration of polysaccharide nano anti-biotic material to be measured like this is respectively 128,64,32,16 ... 2.5 μ g/ml.Minimal inhibitory concentration MIC (Minimal Inhibitory Concentration) is exactly the minimum antibacterial concentration that can stop 50% above bacterial growth.Flat board is scanned under 490nm with microplate reader, MIC determines according to the low Cmin calculating more than 50% of muddy degree than control wells (11-holes).Never get 10 microlitres in the content in the plate well of bacterial growth and be applied on the MH agar plate, cultivated 18 hours down, determine the MBC value of antibacterial for 37 ℃ with this.Minimal bactericidal concentration MBC (Minimal BactericidalConcentration) is exactly the least concentration that can suppress the antibacterial of any remaining colony growth.
Table 2 is polysaccharide nano anti-biotic material and the external fungistatic effect of positive control chitosan drug sensitive test (ug/ml).Experimental result shows that the polysaccharide nano anti-biotic material can effectively suppress the growth of harmful bacterium such as gram positive bacteria and gram negative bacteria, and minimal inhibitory concentration is between 1/32-1ug/ml; Polysaccharide nano anti-biotic material solvent has considerable influence to bacteriostatic activity, is dissolved in having significant fungistatic effect in 0.5% acetum; Polysaccharide nano anti-biotic material fungistatic effect and solution pH value (4.5-7.5) are negative correlation.
Table 1 polysaccharide nano anti-biotic material treatment piglet diarrhea experiment effect
Table 2 chitosan, CSN, the external fungistatic effect of CSN modified product (ug/ml)
CS is the chitosan positive control, and CSM is the polysaccharide nano anti-biotic material according to preparation method preparation of the present invention.
Claims (10)
1. a polysaccharide nano anti-biotic material is characterized in that it is the carrying metal ion chitin nanometer, particle diameter 20-500nm, and wherein the molecular weight of chitosan is 2～80kDa, and deacetylation is 50～100%, and the metal ion weight content is 1～30%.
2. the preparation method of the described polysaccharide nano anti-biotic material of claim 1, it is characterized in that under 20-60 ℃ of stirring, adding molecular weight in dilute acid soln is 2～80kDa, deacetylation is 50～100% chitosans, configuration 0.1%～5% chitosan acid solution, add 0.1～5% cross-linking agent solution to the chitosan acid solution then, in the course of reaction, adding concentration simultaneously is 100～1000mg/L metal ion solution, after reacting completely, centrifugalize, the precipitate distilled water wash is to neutral, and lyophilization promptly gets the polysaccharide nano anti-biotic material.
3. the preparation method of polysaccharide nano anti-biotic material according to claim 2 is characterized in that said diluted acid is acetic acid, acetic acid or hydrochloric acid.
4. the preparation method of polysaccharide nano anti-biotic material according to claim 2 is characterized in that said cross-linking agent is the anion cross-linking agent, comprises sodium polyphosphate, sodium sulfate or sodium citrate.
5. the preparation method of polysaccharide nano anti-biotic material according to claim 2 is characterized in that said metal ion solution is sulfate, hydrochlorate, the nitrate aqueous solution of copper ion, zinc ion or is the nitrate aqueous solution of silver ion.
6. the preparation method of the described polysaccharide nano anti-biotic material of claim 1, it is characterized in that under 20-60 ℃ of stirring, adding molecular weight in dilute acid soln is 2～80kDa, deacetylation is 50～100% chitosans, configuration 0.1%～5% chitosan acid solution, add 0.1～5% cross-linking agent solution to the chitosan acid solution then, form microemulsion, centrifugalize, the rinsing of precipitate distilled water is to neutral, and lyophilization gets chitin nanometer, chitin nanometer dry powder being placed concentration again is 100～1000mg/L metal ion solution, vibration absorption places oven for drying with the chitin nanometer after the absorption, promptly gets the polysaccharide nano anti-biotic material.
7. the preparation method of polysaccharide nano anti-biotic material according to claim 6 is characterized in that said diluted acid is acetic acid, acetic acid or hydrochloric acid.
8. the preparation method of polysaccharide nano anti-biotic material according to claim 6 is characterized in that said cross-linking agent is the anion cross-linking agent, comprises sodium polyphosphate, sodium sulfate or sodium citrate.
9. the preparation method of polysaccharide nano anti-biotic material according to claim 6 is characterized in that said metal ion solution is sulfate, hydrochlorate, the nitrate aqueous solution of copper ion, zinc ion or is the nitrate aqueous solution of silver ion.
10. according to claim 1 or 2 or 6 described polysaccharide nano anti-biotic materials, it is characterized in that as antibiotic, antiviral drugs or feed additive.
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| WO2008089628A1 (en) * | 2007-01-18 | 2008-07-31 | Ningbo Puai Bioengineering Co., Ltd. | A nanoparticle of glucidamin for treating tumor and preparation method thereof |
| CN102125203A (en) * | 2010-12-23 | 2011-07-20 | 宁波普爱生物工程有限公司 | Glycosaminoglycan ultrafine particle-containing health food and production method thereof |
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| WO2008089628A1 (en) * | 2007-01-18 | 2008-07-31 | Ningbo Puai Bioengineering Co., Ltd. | A nanoparticle of glucidamin for treating tumor and preparation method thereof |
| US20100069324A1 (en) * | 2007-01-18 | 2010-03-18 | Ningbo Puai Bioengineering Co., Ltd. | Nanoparticle of glucidamin for treating tumor and preparation method thereof |
| JP2010516634A (en) * | 2007-01-18 | 2010-05-20 | ニングボ プアイ バイオエンジニアリング シーオー．， エルティーディー． | Nanoparticles for tumor treatment comprising glucidamine and preparation method thereof |
| US8828968B2 (en) * | 2007-01-18 | 2014-09-09 | Ningbo Puai Bioengineering Co., Ltd. | Nanoparticle of glucidamin for treating tumor and preparation method thereof |
| CN102125203A (en) * | 2010-12-23 | 2011-07-20 | 宁波普爱生物工程有限公司 | Glycosaminoglycan ultrafine particle-containing health food and production method thereof |
| CN102125203B (en) * | 2010-12-23 | 2013-07-31 | 宁波普爱生物工程有限公司 | Glycosaminoglycan ultrafine particle-containing health food and production method thereof |
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| CN107502488A (en) * | 2017-08-07 | 2017-12-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of antibiotic skin-care soap and products thereof |
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| CN110804247B (en) * | 2019-11-26 | 2022-04-15 | 泉州师范学院 | Chitosan microsphere-loaded nano-silver antibacterial polypropylene material, composite antibacterial agent and preparation method thereof |
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