CN102327284A - Liquid-phase synthesis method of silver-chitosan and/or chitosan derivative nanocomposite - Google Patents
Liquid-phase synthesis method of silver-chitosan and/or chitosan derivative nanocomposite Download PDFInfo
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Abstract
The invention discloses a liquid-phase synthesis method of silver-chitosan and/or chitosan derivative nanocomposite. The obtained product has the functions of promoting wound surface healing, arresting bleeding, relieving pain, resisting inflammation and sterilizing bacteria, is suitable for female vaginitis, cervicitis, cervical erosion, bedsore, dermal ulcer, burn, scald, trauma, other skin phlogosis, tinea of feet and hands and the like, and can also be used for preparing various trauma dressings such as thin films, sponges, suppositories for gynecology, application films and the like.
Description
The application is for dividing an application: the original bill application number: 200910017600.8, and the applying date: 2009.8.11, denomination of invention: the method for preparing and the application of silver, chitosan and/or its derivates nanometer complex.
Technical field
The present invention relates to chemical industry and medical technical field; Particularly relate to the method for preparing of a kind of silver, chitosan and/or the nano combined medicinal powder of chitosan derivatives and, also can be used for preparing various trauma dressings such as thin film, sponge, gynecological with suppository, pad pasting etc. treating women vaginitis, cervicitis, cervical erosion, decubital ulcer, skin ulcer, burn, scald, wound, reaching the application on the medicines such as other scytitiss, tinea manus and pedis.
Background technology
Chitosan is the deacetylated product of chitin, is the alkaline amino property polysaccharide that occurring in nature exists.In recent years; The research of Chinese scholars shows, chitosan and derivant thereof have hemostasis, pain relieving, adjusting macrophage and fibroblast growth and bacteriostasis widely, and; Have and excellent biological compatibility; Therefore, many scholars are with its promoter as wound healing, and various researchs confirm that also chitosan and derivant thereof can promote wound healing.The chitosan of variable concentrations, separate sources and derivant thereof promote fibrocellular propagation on the one hand, and the structure that helps newborn repair tissue is reinvented and made up, and can strengthen or recover the mechanical strength behind the wound healing; Suppress the excessive multiplication of fibroblast on the other hand, prevent scar hyperplasia, help the recovery of outward appearance and function, make wound obtain the high-quality healing.Kweon, (2003), Okamoto (2002; 1995), Ueno (1999) (Kweon DK; Song SB, Park YY. Preparation of water-soluble chitosan/heparin complex and its application as wound healing accelerator. Biomaterials. 2003 Apr; 24 (9): 1595-601; Okamoto Y; Watanabe M; Miyatake K; Morimoto M, Shigemasa Y, Minami S. Effects of chitin/chitosan and their oligomers/monomers on migrations of fibroblasts and vascular endothelium.Biomaterials. 2002 May; 23 (9): 1975-9; Okamoto Y; Shibazaki K, Minami S, Matsuhashi A; Tanioka S, Shigemasa Y. Evaluation of chitin and chitosan on open would healing in dogs.J Vet Med Sci. 1995 Oct; 57 (5): 851-4; Ueno H; Yamada H, Tanaka I, Kaba N; Matsuura M; Okumura M, Kadosawa T, Fujinaga T. Accelerating effects of chitosan for healing at early phase of experimental open wound in dogs. Biomaterials. 1999 Aug; 20 (15): 1407-14.) wait and to find all that in experiment chitosan can promote animal skin site of injury epithelization, form granulation tissue, promote the infiltration and the synthetic collagen of fibroblast of polymorphonuclear cell, thereby promote wound healing.(2006) (Wittaya-Areekul S, Prahsarn C. Development and in vitro evaluation of chitosan-polysaccharides composite wound dressings. 2006 Feb 17 such as Wittaya-Areekul S; ) be raw material with the chitosan, add corn starch or dextran, the chitosan wound dressing of preparation has preferable characteristic; Liu Dewu (Liu Dewu; Several kinds of biomaterials are to the synthetic influence of human epidermal cell DNA, biomedical engineering and clinical .2003,7 (3) .133-134
)Result of study confirm that chitosan has a facilitation to human epidermal cell DNA is synthetic.Report such as Wang Xiaoqin (
The kingDawn celery, Wang Guibo etc., the dressing of chitosan gum protozoa is to the influence and the meaning of deep lipid peroxidation, Chinese clinical rehabilitation .2002,6 (14) .2075-2076.Wang Xiuqin, Lin Li, Wang Xiaoqin; Li Xiaohui; Back deep NO is used in the dressing of chitosan gum protozoa and NOS changes and meaning, Chinese medical writing magazine .2003,10 (5) .404-407); Chitosan and Mus tail collagen are made into dressing stock solution by 1:9 and 1:1 respectively and process the dressing of chitosan gum protozoa, chitosan gum protozoa dressing group each the time to put the wound healing rate mutually high than the normal healing group; The dressing of chitosan gum protozoa has the promoting healing effect and is dosage correlation rat deep ii degree burn wound surface; After using the dressing of chitosan gum protozoa, wound surface lipid peroxidation degree alleviates, EGF and bFGF express strengthen, nitric oxide (NO) content and the active reduction of nitricoxide synthase (NOS).Zoopery and clinical practice show that all chitosan is effective to chronic and refractory, contaminated wound.
That nanometer silver has is more antibacterial, bactericidal action and broad-spectrum antibacterial activity thereof; And because quantum effect, small-size effect and have great specific surface area; Thereby have the incomparable antibacterial effect of traditional inorganic antiseptic, become very promising antibacterials of new generation.Nanometer silver is also extensive day by day in the application of aspects such as medical catheter, operating theater instruments, dental antibacterial material, healthy reproduction, family planning apparatus and wound dressing as anti-biotic material, in the prospect of medical domain extensive application.With chitosan and derivant thereof as carrier, dispersant and protectant silver---the method for preparing of chitosan and derivates nanometer complex powder thereof and use and do not appear in the newspapers.
Summary of the invention
To the deficiency of prior art, one of the object of the invention provides a kind of silver, chitosan and/or chitosan derivatives nano-complex and preparation method thereof.
Two of the object of the invention provides the application in the medicine of preparation treatment skin ulcer, decubital ulcer, burn, treatment women vaginitis, cervicitis, cervical erosion, scytitis, tinea manus and pedis etc. of above-mentioned silver, chitosan and derivates nanometer complex powder thereof.
Three of the object of the invention provides above-mentioned silver, chitosan and derivates nanometer complex powder thereof and is preparing various trauma dressings such as thin film, sponge, gynecological with the application in suppository, the pad pasting etc.
Technical scheme of the present invention is:
A kind of silver, chitosan and/or chitosan derivatives nano-complex adopt the solid-phase synthesis preparation, and step is following:
(1) chitosan and chitosan derivatives grinding are fine powder;
(2) silver nitrate being ground is fine powder;
(3) with chitosan and/or chitosan derivatives fine powder and silver nitrate fine powder mixing; Fully ground 1～3 hour; The part by weight of chitosan and/or chitosan derivatives and silver nitrate be 100:0.0005～0.5 (preferred: 100:0.005～0.3, more preferably: 100:0.05～0.2);
(4) add Reducing agent, Reducing agent is 1:1～2:1 with the reducing equivalent ratio of silver nitrate, fully grinds 2～6 hours, promptly gets silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Said chitosan derivatives is a kind of in hydroxypropyl chitosan, Chitofilmer, carboxymethyl chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl chitin or several;
Said Reducing agent is glucose, N-acetylglucosamine, sodium citrate, ascorbic acid, arabo-ascorbic acid, hydrazine hydrate, formaldehyde, dextrin or dextran etc.
Another kind of different techniques scheme of the present invention is:
A kind of silver, chitosan and/or chitosan derivatives nano-complex adopt the solid-phase synthesis preparation, and step is following:
(1) chitosan and chitosan derivatives grinding are fine powder;
(2) silver nitrate being ground is fine powder;
(3) with chitosan and/or chitosan derivatives fine powder and silver nitrate fine powder mixing; Fully ground 1～3 hour; The part by weight of chitosan and/or chitosan derivatives and silver nitrate be 100:0.0005～0.5 (preferred: 100:0.005～0.3, more preferably: 100:0.05～0.2);
(4) fine powder that step (3) is obtained further ground 1～6 hour, was exposed under the light source 24～48 hours, promptly got silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Said chitosan derivatives is a kind of in hydroxypropyl chitosan, Chitofilmer, carboxymethyl chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl chitin or several,
Said light source is iodine-tungsten lamp light, ultraviolet light or natural light.
Another kind of different techniques scheme of the present invention is:
A kind of silver, chitosan and/or chitosan derivatives nano-complex adopt the liquid phase synthesizing method preparation, and step is following:
(1) chitosan and/or chitosan derivatives are dissolved in slightly acidic water solution or water, fully stir, making its mass concentration is 1～3%;
(2) with silver nitrate be configured to mass concentration be 0.001～1% (preferred: 0.01～0.5%, more preferably: silver nitrate aqueous solution 0.1～0.5%) or silver-colored ammonia spirit;
(3) under vigorous stirring; The silver nitrate aqueous solution or the silver-colored ammonia spirit that in step (1) gained solution, dropwise slowly add step (2) gained; The part by weight of chitosan and/or chitosan derivatives and silver nitrate is that 100:0.0005～0.5 is (preferred: 100:0.005～0.3; More preferably: 100:0.05～0.2), after being added dropwise to complete, continued stirring reaction 1～6 hour;
(4) under vigorous stirring, dropwise slowly add the Reducing agent aqueous solution to step (3) gained solution, Reducing agent is 1:1～2:1 with the reducing equivalent ratio of silver nitrate, after being added dropwise to complete, continues stirring reaction 1～6 hour;
Said chitosan derivatives is a kind of in hydroxypropyl chitosan, Chitofilmer, carboxymethyl chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl chitin or several,
Said Reducing agent aqueous solution is: the aqueous solution of glucose, N-acetylglucosamine, sodium citrate, ascorbic acid, arabo-ascorbic acid, hydrazine hydrate, formaldehyde, dextrin or dextran etc.;
(5) add the organic solvent deposit dehydration to step (4) gained solution, be dried to powder, promptly get silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm.
Foregoing silver, chitosan and/or chitosan derivatives nano-complex, in preferred scheme, slightly acidic water solution described in the step (1) is that mass concentration is 0.5%～1% aqueous acetic acid.
Foregoing silver, chitosan and/or chitosan derivatives nano-complex, in preferred scheme, organic solvent is ethanol or acetone etc. described in the step (5).
Another kind of different techniques scheme of the present invention is:
A kind of silver, chitosan and/or chitosan derivatives nano-complex adopt the liquid phase synthesizing method preparation, and step is following:
(1) with chitosan and/or chitosan derivatives is water-soluble or slightly acidic water solution, fully stir, making its mass concentration is 1～3%;
(2) with silver nitrate be configured to mass concentration be 0.001～1% (preferred: 0.01～0.5%, more preferably: silver nitrate aqueous solution 0.1～0.3%) or silver-colored ammonia spirit;
(3) under vigorous stirring; The silver nitrate aqueous solution or the silver-colored ammonia spirit that in step (1) gained solution, dropwise slowly add step (2) gained; The part by weight of chitosan and/or chitosan derivatives and silver nitrate is that 100:0.0005～0.5 is (preferred: 100:0.005～0.3; More preferably: 100:0.05～0.2), after being added dropwise to complete, continued stirring reaction 1～6 hour;
(4) add the organic solvent deposit dehydration to step (3) gained solution, be dried to powder, be exposed under the light source 24～48 hours, promptly get silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Said chitosan derivatives is a kind of in hydroxypropyl chitosan, Chitofilmer, carboxymethyl chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl chitin or several,
Said light source is iodine-tungsten lamp light, ultraviolet light or natural light.
Foregoing silver, chitosan and/or chitosan derivatives nano-complex, in preferred scheme, the said organic solvent of step (4) is ethanol or acetone etc.
Foregoing silver, chitosan and/or chitosan derivatives nano-complex, chitosan and/or chitosan derivatives are both as stabilizing agent and dispersant, also as functional mass.
The application on the medicine of preparation treatment vaginitis, cervicitis, cervical erosion, decubital ulcer, skin ulcer, burn, scald, wound, scytitis, tinea manus and pedis of described silver, chitosan and/or chitosan derivatives nano-complex.
Described silver, chitosan and/or chitosan derivatives nano-complex are preparing various trauma dressings such as thin film, sponge, gynecological with the application in suppository, the pad pasting.
Above-mentioned silver, chitosan and derivates nanometer complex thereof, its main component are chitosan or chitosan derivatives and nanometer silver, chitosan and derivant thereof in the preparation process promptly as stabilizing agent, dispersant, also as functional mass.The gained complex has has a broad antifungal spectrum, efficient, nontoxic, antibiotic lasting, hemostasis and pain-relieving, promotion wound repair, ulcer healing and air permeability and good is arranged and hygroscopicity.Can accelerate the healing of wound surface such as skin ulcer, decubital ulcer, burn, improve healing quality, reduce toxic and side effects, reduce antibiotic use, prevent the drug-fast generation of bacterial antibiotic secondary.Also can be used for preparing various trauma dressings such as thin film, sponge, gynecological with suppository, pad pasting etc.
In addition, excellent results of the present invention also shows:
1,The function and the advantage that have nanometer silver preparation and chitosan or derivatives thereof simultaneously.
2,In the preparation process with the chitosan or derivatives thereof as Ag
+Carrier, Ag
+At first with the effect of chitosan or derivatives thereof; Generate coordination compound or silver salt; Make its dispersion more even, generate nano-Ag particles in nanometer scale and epigranular after adding Reducing agent or being exposed to light source, the chitosan or derivatives thereof has protective effect to the nano silver particles that generates.
The specific embodiment
Specify technical scheme of the present invention below in conjunction with embodiment, but protection domain is not limited thereto.
One, the solid phase synthesis (chemical reduction method) of silver, chitosan and/or chitosan derivatives nano-complex.
Embodiment 1
A kind of silver, chitosan nano complex, the method for preparing step is following:
(1) the 10g chitosan being ground is fine powder;
(2) the 0.005g silver nitrate being ground is fine powder;
(3) with chitosan fine powder and silver nitrate fine powder mixing, fully ground 1 hour;
(4) add ascorbic acid 0.005 gram, continue fully to grind 2 hours, promptly get silver, chitosan nano complex (sample 1) that silver granuel directly is 1～100nm.
Embodiment 2
A kind of silver, chitosan derivatives nano-complex, the method for preparing step is following:
(1) the 10g carboxymethyl chitosan being ground is fine powder;
(2) the 0.005g silver nitrate being ground is fine powder;
(3) with carboxymethyl chitosan fine powder and silver nitrate fine powder mixing, fully ground 2 hours;
(4) add glucose 0.005 gram, continue fully to grind 2.5 hours, promptly get silver, chitosan derivatives nano-complex (sample 2) that silver granuel directly is 1～100nm.
Embodiment 3
A kind of silver, chitosan and chitosan derivatives nano-complex, the method for preparing step is following:
(1) 7g chitosan and the grinding of 3g hydroxypropyl chitosan are fine powder;
(2) the 0.005g silver nitrate being ground is fine powder;
(3) with chitosan and hydroxypropyl chitosan fine powder and silver nitrate fine powder mixing, fully ground 2 hours;
(4) add N-acetylglucosamine 0.005 gram, continue fully to grind 6 hours, promptly get silver, chitosan and chitosan derivatives nano-complex that silver granuel directly is 1～100nm.
Embodiment 4
A kind of silver, chitosan derivatives nano-complex, the method for preparing step is following:
(1) the 10g Chitofilmer being ground is fine powder;
(2) the 0.01g silver nitrate being ground is fine powder;
(3) with Chitofilmer fine powder and silver nitrate fine powder mixing, fully ground 1 hour;
(4) add sodium citrate 0.01 gram, continue fully to grind 2 hours, promptly get silver, chitosan derivatives nano-complex (sample 3) that silver granuel directly is 1～100nm.
Embodiment 5
A kind of silver, chitosan and chitosan derivatives nano-complex, the method for preparing step is following:
(1) 3g chitosan, 3g hydroxypropyl chitosan and 4g succinyl chitin being ground is fine powder;
(2) the 0.005g silver nitrate being ground is fine powder;
(3) with chitosan, hydroxypropyl chitosan and succinyl chitin fine powder and silver nitrate fine powder mixing, fully ground 3 hours;
(4) add hydrazine hydrate 0.002 gram, continue fully to grind 4 hours, promptly get silver, chitosan and chitosan derivatives nano-complex that silver granuel directly is 1～100nm.
Embodiment 6
A kind of silver, chitosan derivatives nano-complex, the method for preparing step is following:
(1) 6g carboxymethyl chitin and the grinding of 4g succinyl chitin are fine powder;
(2) the 0.009g silver nitrate being ground is fine powder;
(3) with carboxymethyl chitin and succinyl chitin fine powder and silver nitrate fine powder mixing, fully ground 2.5 hours;
(4) add dextrin 0.5 gram, continue fully to grind 4.5 hours, promptly get silver, chitosan derivatives nano-complex that silver granuel directly is 1～100nm.
Two, the solid phase synthesis (photoreduction met hod) of silver, chitosan and/or chitosan derivatives nano-complex.
Embodiment 7
A kind of silver, chitosan nano complex, the method for preparing step is following:
(1) the 100g chitosan being ground is fine powder;
(2) the 0.0005g silver nitrate being ground is fine powder;
(3) with chitosan fine powder and silver nitrate fine powder mixing, fully ground 2 hours;
(4) fine powder that step (3) is obtained further ground 3 hours, was exposed to iodine-tungsten lamp light following 24 hours, promptly got silver, chitosan nano complex that silver granuel directly is 1～100nm.
Embodiment 8
A kind of silver, chitosan derivatives nano-complex, the method for preparing step is following:
(1) the 100g succinyl-chitosan being ground is fine powder;
(2) the 0.008g silver nitrate being ground is fine powder;
(3) with succinyl-chitosan fine powder and silver nitrate fine powder mixing, fully ground 3 hours;
(4) fine powder that step (3) is obtained further ground 3.5 hours, was exposed to ultraviolet light following 24 hours, promptly got silver, chitosan derivatives nano-complex that silver granuel directly is 1～100nm.
Embodiment 9
A kind of silver, chitosan and chitosan derivatives nano-complex, the method for preparing step is following:
(1) 50g chitosan, 20g succinyl-chitosan and 30g carboxymethyl chitosan being ground is fine powder;
(2) the 0.05g silver nitrate being ground is fine powder;
(3) with chitosan, succinyl-chitosan and carboxymethyl chitosan fine powder and silver nitrate fine powder mixing, fully ground 1 hour;
(4) fine powder that step (3) is obtained further ground 6 hours, was exposed to natural light following 36 hours, promptly got silver, chitosan and chitosan derivatives nano-complex (sample 4) that silver granuel directly is 1～100nm.
Embodiment 10
A kind of silver, chitosan derivatives nano-complex, the method for preparing step is following:
(1) 70g hydroxypropyl chitosan and the grinding of 30g carboxymethyl chitin are fine powder;
(2) the 0.3g silver nitrate being ground is fine powder;
(3) with hydroxypropyl chitosan and carboxymethyl chitin fine powder and silver nitrate fine powder mixing, fully ground 2 hours;
(4) fine powder that step (3) is obtained further ground 4 hours, was exposed to natural light following 48 hours, promptly got silver, chitosan derivatives nano-complex (sample 5) that silver granuel directly is 1～100nm.
Three, the liquid phase of silver, chitosan and/or chitosan derivatives nano-complex synthetic (chemical reduction method).
Embodiment 11
A kind of silver, chitosan nano complex, the method for preparing step is following:
(1) the 2g chitosan being dissolved in mass concentration is in the 0.5% 100ml aqueous acetic acid, fully stirring and dissolving;
(2) accurately take by weighing silver nitrate 0.001 and restrain in another beaker adding distil water 50ml, stirring and dissolving;
(3) under vigorous stirring, in step (1) gained solution, dropwise slowly add the silver nitrate aqueous solution of step (2) gained, after being added dropwise to complete, continued stirring reaction 1 hour;
(4) accurately take by weighing ascorbic acid 0.001 and restrain in a beaker, adding distil water 50ml stirring and dissolving; Under vigorous stirring, dropwise slowly add aqueous ascorbic acid to step (3) gained solution, after being added dropwise to complete, continued stirring reaction 2 hours;
(5) add the dehydration of 1000ml95% ethanol precipitation to step (4) gained solution, be dried to powder, promptly get silver, chitosan nano complex (sample 6) that silver granuel directly is 1～100nm.
Embodiment 12
A kind of silver, chitosan derivatives nano-complex, the method for preparing step is following:
(1) 1.5g hydroxypropyl chitosan and 0.5g succinyl-chitosan being dissolved in mass concentration is in the 1% 100ml aqueous acetic acid, fully stirring and dissolving;
(2) accurately take by weighing silver nitrate 0.0001 and restrain in another beaker adding distil water 10ml, stirring and dissolving;
(3) under vigorous stirring, in step (1) gained solution, dropwise slowly add the silver nitrate aqueous solution of step (2) gained, after being added dropwise to complete, continued stirring reaction 3 hours;
(4) accurately take by weighing formaldehyde 0.0001 and restrain in a beaker, adding distil water 100ml stirring and dissolving; Under vigorous stirring, dropwise slowly add formalin to step (3) gained solution, after being added dropwise to complete, continued stirring reaction 4 hours;
(5) add the dehydration of 1000ml acetone precipitation to step (4) gained solution, be dried to powder, promptly get silver, chitosan nano complex that silver granuel directly is 1～100nm.
Embodiment 13
A kind of silver, chitosan and chitosan derivatives nano-complex, the method for preparing step is following:
(1) 1g chitosan, 1g Chitofilmer and 1g succinyl-chitosan are dissolved in the 100ml distilled water, fully stirring and dissolving;
(2) accurately take by weighing silver nitrate 0.01 and restrain in another beaker adding distil water 10ml, stirring and dissolving;
(3) under vigorous stirring, in step (1) gained solution, dropwise slowly add the silver nitrate aqueous solution of step (2) gained, after being added dropwise to complete, continued stirring reaction 6 hours;
(4) accurately take by weighing arabo-ascorbic acid 0.01 and restrain in a beaker, adding distil water 100ml stirring and dissolving; Under vigorous stirring, dropwise slowly add the arabo-ascorbic acid aqueous solution to step (3) gained solution, after being added dropwise to complete, continued stirring reaction 6 hours;
(5) add the dehydration of 1000ml95% ethanol precipitation to step (4) gained solution, vacuum drying becomes powder, promptly gets silver, chitosan and chitosan derivatives nano-complex (sample 7) that silver granuel directly is 1～100nm.
Embodiment 14
Accurately take by weighing chitosan powder 2 and restrain in beaker, add 0.5% aqueous acetic acid 100ml, stirring and dissolving; Accurately take by weighing silver nitrate 0.001 and restrain in another beaker, add 5% ammonia spirit 50ml, stirring and dissolving; Accurately take by weighing ascorbic acid 0.001 and restrain in a beaker, adding distil water 50ml stirring and dissolving; Silver-colored ammonia spirit is dropwise slowly added in the chitosan solution, stirred 1 hour fast simultaneously; Ascorbic acid solution is dropwise added again, stir fast after 1～6 hour simultaneously, adding 1000ml95% ethanol must precipitate, and vacuum drying makes silver---chitosan and derivates nanometer complex powder 13 thereof.
Embodiment 15
Accurately take by weighing carboxymethyl chitosan powder 2 and restrain in beaker, adding distil water 100ml, stirring and dissolving; Accurately take by weighing silver nitrate 0.001 and restrain in another beaker, add 5% ammonia spirit 50ml, stirring and dissolving; Accurately take by weighing ascorbic acid 0.001 and restrain in a beaker, adding distil water 50ml stirring and dissolving; Silver-colored ammonia spirit liquid is dropwise slowly added in the carboxymethyl chitosan sugar juice, stirred 1 hour fast simultaneously; Ascorbic acid solution is dropwise added again, stir fast after 1～6 hour simultaneously, adding 1000ml95% ethanol must precipitate, and vacuum drying makes silver---chitosan and derivates nanometer complex powder 14 thereof.
Four, the liquid phase of silver, chitosan and/or chitosan derivatives nano-complex synthetic (photoreduction met hod).
Embodiment 16
Accurately take by weighing chitosan powder, succinyl-chitosan, each 0.5g of succinyl chitin in beaker, add 0.5% aqueous acetic acid 100ml, stirring and dissolving; Accurately take by weighing silver nitrate 0.001 and restrain in another beaker adding distil water 50ml, stirring and dissolving; Silver nitrate solution is dropwise slowly added in the chitosan solution, stirred 1～6 hour fast simultaneously; Adding 750ml95% ethanol must precipitate, and vacuum drying in the horizontalization ware, was exposed to light source 24 hours, made silver, chitosan and derivates nanometer complex thereof (sample 8).
Embodiment 17
Accurately take by weighing carboxymethyl chitosan powder 2 and restrain in beaker, adding distil water 100ml, stirring and dissolving; Accurately take by weighing silver nitrate 0.001 and restrain in another beaker adding distil water 50ml, stirring and dissolving; Silver nitrate solution is dropwise slowly added in the carboxymethyl chitosan sugar juice, stirred 1～6 hour fast simultaneously; Adding 750ml acetone must precipitate, and vacuum drying in the horizontalization ware, was exposed to ultraviolet light 48 hours, made silver, the nano combined medicinal powder of chitosan derivatives.
Embodiment 18
Accurately take by weighing chitosan powder 2 and restrain in beaker, add 0.5% aqueous acetic acid 100ml, stirring and dissolving; Accurately take by weighing silver nitrate 0.001 and restrain in another beaker, add 5% ammonia spirit 50ml, stirring and dissolving; Silver-colored ammonia spirit is dropwise slowly added in the chitosan solution, stirred 1 hour fast simultaneously; Adding 750ml95% ethanol must precipitate, and vacuum drying in the horizontalization ware, was exposed to iodine-tungsten lamp light 36 hours, made silver, chitosan nano complex powder (sample 9).
Embodiment 19
Each 1 restrains in beaker adding distil water 100ml, stirring and dissolving accurately to take by weighing carboxymethyl chitosan powder, carboxymethyl chitin; Accurately take by weighing silver nitrate 0.001 and restrain in another beaker, add 5% ammonia spirit 50ml, stirring and dissolving; Silver-colored ammonia spirit is dropwise slowly added in the carboxymethyl chitosan sugar juice, stirred 1 hour fast simultaneously; Adding 750ml95% ethanol must precipitate, and vacuum drying in the horizontalization ware, was exposed to lamp 24 hours, made silver, the nano combined medicinal powder of chitosan derivatives (sample 10).
Test Example 1
The ultraviolet-visual spectrum analysis of sample 1-10 nano silver particles of the present invention: the result sees table 1.
Table 1: the ultraviolet-visual spectrum analysis of sample nano silver particles:
Can be known by table 1: metal nanoparticle has absorption band or uptake zone in the ultraviolet-visible district, and the uv absorption peak position of nano silver particles is generally about 410 nm.Therefore think the nanometer silver epigranular of this method preparation, silver granuel footpath and in 1～100nm nanometer.
Test Example 2
Sample 1-10 bacteriostasis of the present invention research: G
=Coccus: staphylococcus aureus; G
-Bacillus: escherichia coli, bacillus pyocyaneus.
Get 13 test tubes of sterilization that the 1.0ml nutrient broth is housed and number 1,2,3 respectively ... ..13; Other gets 1 empty test tube of sterilization as blank pipe numbering 14; In the 1st pipe, add the 1.0ml sample solution, get 1.0ml behind the mixing and add in the 2nd pipe, be diluted to the 12nd pipe with method.The 13rd pipe does not add medicinal liquid and makes the positive control pipe.From manage 12 pipes, draw 1.0 mixed liquors and in the 14th pipe, make negative control.Get 10
6Cfu/ml bacterium liquid 0.1ml adds respectively in 1～13 developmental tube and shakes up, and the above-mentioned developmental tube of respectively organizing is put in 30～35 ℃ of incubators and cultivated 16～24h, and the solution clarification is minimum inhibitory concentration (M IC); Get solution and clarify 0. 1ml, be inoculated into the required nutrient agar plate medium surface of each bacterium, evenly with the coating of aseptic L rod; Each concentration inoculation 3～4 flat board; Culture put in 37 ℃ of calorstats cultivate, behind 24 h, not having colony growth is minimum antibacterial dense (MBC).
Fungus: Candida albicans: press pharmacological experiment methodology (Xu Shuyun; Bian Rulian, the Chen Xiu chief editor. the pharmacological experiment methodology. Beijing: People's Health Publisher, the third edition; 2006:1705-1717), record minimum inhibitory concentration (M IC) and minimum antibacterial dense (MFC).The result shows: silver, chitosan and derivates nanometer complex powder sample thereof are to gram positive bacteria (its representative strain is a staphylococcus aureus) and gram negative bacteria (its representative strain is enterobacteria, bacillus pyocyaneus); And fungus (its representative strain is a Candida albicans) all has the good sterilization effect, and the result is as shown in table 2.Staphylococcus aureus, escherichia coli, bacillus pyocyaneus, Candida albicans are surgery, skin, and gynecological infection (like vaginitis, cervicitis, cervical erosion, decubital ulcer, skin ulcer, burn, scald, wound, scytitis, tinea manus and pedis) common pathogen kind.
Table 2: sample bacteriostasis research (sample Ag concentration: μ g/ml)
Should be pointed out that then with embodiment be the more representational example of the present invention, obvious technical scheme of the present invention is not limited to the foregoing description.A lot of distortion can also be arranged.From then on those of ordinary skill in the art with disclosed can mention or it is associated in the invention, all should think the claimed scope of this patent.
Claims (3)
1. the method for preparing of a silver, chitosan and/or chitosan derivatives nano-complex is characterized in that, adopts the liquid phase synthesizing method preparation, and step is following:
(1) with chitosan and/or chitosan derivatives is water-soluble or slightly acidic water solution, fully stir, making its mass concentration is 1～3%;
(2) silver nitrate being configured to mass concentration is 0.001～1% silver nitrate aqueous solution or silver-colored ammonia spirit;
(3) under vigorous stirring; The silver nitrate aqueous solution or the silver-colored ammonia spirit that in step (1) gained solution, dropwise slowly add step (2) gained; The part by weight of chitosan and/or chitosan derivatives and silver nitrate is 100:0.0005～0.5; After being added dropwise to complete, continued stirring reaction 1～6 hour;
(4) under vigorous stirring, dropwise slowly add the Reducing agent aqueous solution to step (3) gained solution, Reducing agent is 1:1～2:1 with the reducing equivalent ratio of silver nitrate, after being added dropwise to complete, continues stirring reaction 1～6 hour;
(5) add the organic solvent deposit dehydration to step (4) gained solution, be dried to powder, promptly get silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Said chitosan derivatives is a kind of in hydroxypropyl chitosan, Chitofilmer, carboxymethyl chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl chitin or several; Said Reducing agent aqueous solution is: the aqueous solution of glucose, N-acetylglucosamine, sodium citrate, ascorbic acid, arabo-ascorbic acid, hydrazine hydrate, formaldehyde, dextrin or dextran.
2. method for preparing according to claim 1 is characterized in that, slightly acidic water solution described in the step (1) is that mass concentration is 0.5%～1% aqueous acetic acid.
3. method for preparing according to claim 1 is characterized in that, organic solvent is ethanol or acetone described in the step (5).
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