CN102382332B - Method for liquid-phase synthesis of nano complex of silver, chitosan and/or chitosan derivatives - Google Patents
Method for liquid-phase synthesis of nano complex of silver, chitosan and/or chitosan derivatives Download PDFInfo
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Abstract
The invention discloses a method for liquid-phase synthesis of a nano complex of silver, chitosan and/or chitosan derivatives. The obtained product has the effects of promoting wound surface healing, stopping bleeding, relieving pain, resisting inflammation and killing bacteria, can be used for treating female colpitis, cervicitis and cervical erosion, decubitus, dermal ulcer, burn, scald, wound and other skin inflammation, tinea of feet and hands and the like, and can also be used for preparing various wound dressings such as thin films, sponge, gynecologic suppository, paster 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: preparation method and the application of silver, chitosan and/or its derivates nanometer mixture.
Technical field
The present invention relates to chemical industry and medical technical field, particularly relate to the preparation method of a kind of silver, chitosan and/or the nano combined medicinal powder of chitosan derivatives and treating women vaginitis, cervicitis, cervical erosion, bedsore, skin ulcer, burn, scald, wound, reaching the application on the medicines such as other skin inflammationes, tinea manus and pedis, also can be used for preparing various trauma dressings such as film, sponge, Gynaecological suppository, pad pasting etc.
Background technology
Chitosan is the deacetylated product of chitin, is the alkaline amino polysaccharide that occurring in nature exists.In recent years, studies show that of Chinese scholars, chitosan and derivative thereof have hemostasis, pain relieving, adjusting scavenger cell and fibroblast growth and bacteriostatic action widely, and, have and good biocompatibility, therefore, many scholars are with its promotor as wound healing, and various researchs confirm that also chitosan and derivative thereof can wound healings.The chitosan of different concns, different sources and derivative thereof promote fibrocellular propagation on the one hand, and the structure that is conducive to newborn repair tissue is reinvented and made up, and can strengthen or recover the mechanical strength after the wound healing; Suppress on the other hand the excessive multiplication of fibroblast, prevent scar hyperplasia, be conducive to 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.) etc. find all that in experiment chitosan can promote animal skin site of injury epithelization, form granulation tissue, promote infiltration and the synthetic collagen of inoblast 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; ) take chitosan as raw material, adding W-Gum or dextran, the Chitosan in Wound Dressing of preparation has better characteristic, Liu Dewu (Liu Dewu, the impact that several biomaterials are synthetic on human epidermal cell DNA, biomedical engineering and clinical .2003,7 (3) .133-134
)Result of study confirm that chitosan has a promoter action to human epidermal cell DNA is synthetic.The report such as Wang Xiaoqin (
The kingDawn celery, Wang Guibo etc., the dressing of chitosan gum protista is on impact and the meaning of deepⅱdegreeburnwound peroxidatic reaction of lipid, Chinese Clinical rehabilitation .2002,6 (14) .2075-2076.Wang Xiuqin, Lin Li, Wang Xiaoqin, Li Xiaohui, deepⅱdegreeburnwound NO and NOS changed and meaning after the dressing of chitosan gum protista was used, Chinese medical writing magazine .2003,10 (5) .404-407), chitosan and mouse tail collagen are made into dressing stoste by 1:9 and 1:1 respectively and make the dressing of chitosan gum protista, chitosan gum protista dressing group each the time phase point Wound healing rate high than the normal healing group; The dressing of chitosan gum protista has the promoting healing effect and is dosage correlation the rat deep ii degree burn surface of a wound, after using the dressing of chitosan gum protista, surface of a wound peroxidatic reaction of lipid degree alleviates, EGF and bFGF express strengthen, nitrogen protoxide (NO) content and nitricoxide synthase (NOS) activity decreased.Experimentation on animals and clinical application show that all chitosan is effective to chronic and refractory, contaminated wound.
Nanometer silver has the anti-microbial activity of more antibacterial, germicidal action and wide spectrum 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 increasingly extensive in the application of the aspects such as medical catheter, instruments, dental antibacterial material, healthy reproduction, birth control apparatus and wound dressing as anti-biotic material, in the prospect of medical field extensive application.With chitosan and derivative thereof as carrier, dispersion agent and protectant silver---preparation method and the application of chitosan and derivates nanometer mixture pulvis thereof have no report.
Summary of the invention
For the deficiencies in the prior art, one of purpose of the present invention provides a kind of silver, chitosan and/or chitosan derivatives nano-complex and preparation method thereof.
Two of purpose of the present invention provides the application in the medicine of preparation treatment skin ulcer, bedsore, burn, treatment women vaginitis, cervicitis, cervical erosion, skin inflammation, tinea manus and pedis etc. of above-mentioned silver, chitosan and derivates nanometer mixture pulvis thereof.
Three of purpose of the present invention provides the application in preparing various trauma dressings such as film, sponge, Gynaecological suppository, pad pasting etc. of above-mentioned silver, chitosan and derivates nanometer mixture pulvis thereof.
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 as follows:
(1) chitosan and chitosan derivatives are ground to fine powder;
(2) Silver Nitrate is ground to 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 is that 100:0.0005～0.5(is preferred: 100:0.005～0.3, more preferably: 100:0.05～0.2);
(4) add reductive agent, reductive agent is 1:1～2:1 with the reducing equivalent ratio of Silver Nitrate, fully grinds 2～6 hours, namely gets silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Described chitosan derivatives is one or several in hydroxypropyl chitosan, Hydroxypropyl chitosan, cm-chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl-chitin;
Described reductive agent is glucose, 2-Acetamido-2-deoxy-D-glucose, Trisodium Citrate, xitix, saccharosonic acid, hydrazine hydrate, formaldehyde, dextrin or dextran etc.
The different technical scheme of another kind 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 as follows:
(1) chitosan and chitosan derivatives are ground to fine powder;
(2) Silver Nitrate is ground to 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 is that 100:0.0005～0.5(is 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, namely got silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Described chitosan derivatives is one or several in hydroxypropyl chitosan, Hydroxypropyl chitosan, cm-chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl-chitin,
Described light source is tungsten-iodine lamp light, ultraviolet light or natural light.
The different technical scheme of another kind 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 as follows:
(1) chitosan and/or chitosan derivatives are dissolved in weakly acidic water solution or water, fully stir, making its mass concentration is 1～3%;
(2) Silver Nitrate being configured to mass concentration is that 0.001～1%(is preferred: 0.01～0.5%, more preferably: silver nitrate aqueous solution 0.1～0.5%) or silver-colored ammonia soln;
(3) under vigorous stirring, the silver nitrate aqueous solution or the silver-colored ammonia soln that dropwise slowly add step (2) gained in step (1) the gained solution, 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 reductive agent aqueous solution to step (3) gained solution, reductive 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;
Described chitosan derivatives is one or several in hydroxypropyl chitosan, Hydroxypropyl chitosan, cm-chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl-chitin,
The described reductive agent aqueous solution is: the aqueous solution of glucose, 2-Acetamido-2-deoxy-D-glucose, Trisodium Citrate, xitix, saccharosonic acid, hydrazine hydrate, formaldehyde, dextrin or dextran etc.;
(5) add the organic solvent deposit dehydration to step (4) gained solution, be dried to powder, namely 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, weakly 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).
The different technical scheme of another kind 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 as follows:
(1) with chitosan and/or chitosan derivatives is water-soluble or weakly acidic water solution, fully stir, making its mass concentration is 1～3%;
(2) Silver Nitrate being configured to mass concentration is that 0.001～1%(is preferred: 0.01～0.5%, more preferably: silver nitrate aqueous solution 0.1～0.3%) or silver-colored ammonia soln;
(3) under vigorous stirring, the silver nitrate aqueous solution or the silver-colored ammonia soln that dropwise slowly add step (2) gained in step (1) the gained solution, 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, namely get silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Described chitosan derivatives is one or several in hydroxypropyl chitosan, Hydroxypropyl chitosan, cm-chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl-chitin,
Described light source is tungsten-iodine lamp light, ultraviolet light or natural light.
Foregoing silver, chitosan and/or chitosan derivatives nano-complex, in preferred scheme, the described 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 stablizer and dispersion agent, also as functional mass.
The application on the medicine of preparation treatment vaginitis, cervicitis, cervical erosion, bedsore, skin ulcer, burn, scald, wound, skin inflammation, tinea manus and pedis of described silver, chitosan and/or chitosan derivatives nano-complex.
The application in preparing various trauma dressings such as film, sponge, Gynaecological suppository, pad pasting of described silver, chitosan and/or chitosan derivatives nano-complex.
Above-mentioned silver, chitosan and derivates nanometer mixture thereof, its main component are chitosan or chitosan derivatives and nanometer silver, chitosan and derivative thereof in preparation process namely as stablizer, dispersion agent, also as functional mass.The gained mixture has has a broad antifungal spectrum, efficient, nontoxic, antibiotic lasting, hemostasis and pain-relieving, promotion wound repair, ulcer healing and good ventilation property and water absorbability is arranged.Can accelerate the healing of the surface of a wound such as skin ulcer, bedsore, burn, improve healing quality, reduce toxic side effect, reduce antibiotic use, prevent the generation of bacterial antibiotic secondary resistance.Also can be used for preparing various trauma dressings such as film, sponge, Gynaecological suppository, pad pasting etc.
In addition, excellent results of the present invention also shows:
1,The function and the advantage that have simultaneously nanometer silver preparation and chitosan or derivatives thereof.
2,In preparation process with the chitosan or derivatives thereof as Ag
+Carrier, Ag
+At first with the effect of chitosan or derivatives thereof; generate title complex or silver salt; make its dispersion more even, generate nano-Ag particles in nanometer scale and epigranular after adding reductive agent or being exposed to light source, the chitosan or derivatives thereof has provide protection to the nano silver particles that generates.
Embodiment
Describe technical scheme of the present invention in detail below in conjunction with embodiment, but protection domain is not limited to this.
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 mixture, preparation method's step is as follows:
(1) the 10g chitosan is ground to fine powder;
(2) the 0.005g Silver Nitrate is ground to fine powder;
(3) with chitosan fine powder and Silver Nitrate fine powder mixing, fully ground 1 hour;
(4) add xitix 0.005 gram, continue fully to grind 2 hours, namely get silver, chitosan nano mixture (sample 1) that silver granuel directly is 1～100nm.
Embodiment 2
A kind of silver, chitosan derivatives nano-complex, preparation method's step is as follows:
(1) the 10g cm-chitosan is ground to fine powder;
(2) the 0.005g Silver Nitrate is ground to fine powder;
(3) with cm-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, namely 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, preparation method's step is as follows:
(1) 7g chitosan and 3g hydroxypropyl chitosan are ground to fine powder;
(2) the 0.005g Silver Nitrate is ground to fine powder;
(3) with chitosan and hydroxypropyl chitosan fine powder and Silver Nitrate fine powder mixing, fully ground 2 hours;
(4) add 2-Acetamido-2-deoxy-D-glucose 0.005 gram, continue fully to grind 6 hours, namely 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, preparation method's step is as follows:
(1) the 10g Hydroxypropyl chitosan is ground to fine powder;
(2) the 0.01g Silver Nitrate is ground to fine powder;
(3) with Hydroxypropyl chitosan fine powder and Silver Nitrate fine powder mixing, fully ground 1 hour;
(4) add Trisodium Citrate 0.01 gram, continue fully to grind 2 hours, namely 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, preparation method's step is as follows:
(1) 3g chitosan, 3g hydroxypropyl chitosan and 4g succinyl-chitin are ground to fine powder;
(2) the 0.005g Silver Nitrate is ground to 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, namely 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, preparation method's step is as follows:
(1) 6g carboxymethyl chitin and 4g succinyl-chitin are ground to fine powder;
(2) the 0.009g Silver Nitrate is ground to 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, namely 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 mixture, preparation method's step is as follows:
(1) the 100g chitosan is ground to fine powder;
(2) the 0.0005g Silver Nitrate is ground to 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 tungsten-iodine lamp light lower 24 hours, namely got silver, chitosan nano mixture that silver granuel directly is 1～100nm.
Embodiment 8
A kind of silver, chitosan derivatives nano-complex, preparation method's step is as follows:
(1) the 100g succinyl-chitosan is ground to fine powder;
(2) the 0.008g Silver Nitrate is ground to 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 lower 24 hours, namely 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, preparation method's step is as follows:
(1) 50g chitosan, 20g succinyl-chitosan and 30g cm-chitosan are ground to fine powder;
(2) the 0.05g Silver Nitrate is ground to fine powder;
(3) with chitosan, succinyl-chitosan and cm-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 lower 36 hours, namely 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, preparation method's step is as follows:
(1) 70g hydroxypropyl chitosan and 30g carboxymethyl chitin are ground to fine powder;
(2) the 0.3g Silver Nitrate is ground to 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 lower 48 hours, namely 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 mixture, preparation method's step is as follows:
(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, dropwise slowly add the silver nitrate aqueous solution of step (2) gained in step (1) the gained solution, after being added dropwise to complete, continued stirring reaction 1 hour;
(4) accurately take by weighing xitix 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, namely get silver, chitosan nano mixture (sample 6) that silver granuel directly is 1～100nm.
Embodiment 12
A kind of silver, chitosan derivatives nano-complex, preparation method's step is as follows:
(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, dropwise slowly add the silver nitrate aqueous solution of step (2) gained in step (1) the gained solution, 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, namely get silver, chitosan nano mixture that silver granuel directly is 1～100nm.
Embodiment 13
A kind of silver, chitosan and chitosan derivatives nano-complex, preparation method's step is as follows:
(1) 1g chitosan, 1g Hydroxypropyl chitosan 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, dropwise slowly add the silver nitrate aqueous solution of step (2) gained in step (1) the gained solution, after being added dropwise to complete, continued stirring reaction 6 hours;
(4) accurately take by weighing saccharosonic acid 0.01 and restrain in a beaker, adding distil water 100ml stirring and dissolving; Under vigorous stirring, dropwise slowly add the saccharosonic 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, namely 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 soln 50ml, stirring and dissolving; Accurately take by weighing xitix 0.001 and restrain in a beaker, adding distil water 50ml stirring and dissolving; Silver-colored ammonia soln is dropwise slowly added in the chitosan solution, and rapid stirring is 1 hour simultaneously; Ascorbic acid solution is dropwise added, rapid stirring is after 1～6 hour simultaneously again, and adding 1000ml95% ethanol must precipitate, and vacuum-drying makes silver---chitosan and derivates nanometer mixture pulvis 13 thereof.
Embodiment 15
Accurately take by weighing cm-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 soln 50ml, stirring and dissolving; Accurately take by weighing xitix 0.001 and restrain in a beaker, adding distil water 50ml stirring and dissolving; Silver-colored ammonia soln liquid is dropwise slowly added in the carboxymethyl chitosan sugar soln, and rapid stirring is 1 hour simultaneously; Ascorbic acid solution is dropwise added, rapid stirring is after 1～6 hour simultaneously again, and adding 1000ml95% ethanol must precipitate, and vacuum-drying makes silver---chitosan and derivates nanometer mixture pulvis 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, and rapid stirring is 1～6 hour 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 mixture thereof (sample 8).
Embodiment 17
Accurately take by weighing cm-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 soln, and rapid stirring is 1～6 hour 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 soln 50ml, stirring and dissolving; Silver-colored ammonia soln is dropwise slowly added in the chitosan solution, and rapid stirring is 1 hour simultaneously; Adding 750ml95% ethanol must precipitate, and vacuum-drying in the horizontalization ware, was exposed to tungsten-iodine lamp light 36 hours, made silver, chitosan nano mixture pulvis (sample 9).
Embodiment 19
Each 1 restrains in beaker adding distil water 100ml, stirring and dissolving accurately to take by weighing cm-chitosan powder, carboxymethyl chitin; Accurately take by weighing Silver Nitrate 0.001 and restrain in another beaker, add 5% ammonia soln 50ml, stirring and dissolving; Silver-colored ammonia soln is dropwise slowly added in the carboxymethyl chitosan sugar soln, and rapid stirring is 1 hour 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 results are shown in Table 1.
Table 1: the ultraviolet-visual spectrum analysis of sample nano silver particles:
As shown in Table 1: metal nanoparticle has absorption band or uptake zone in the ultraviolet-visible district, and the uv-absorbing peak position of nano silver particles is generally about 410 nm.Therefore think the nanometer silver epigranular of the method preparation, silver granuel footpath and in 1～100nm nanometer.
Test example 2
Sample 1-10 bacteriostatic action of the present invention research: G
=Coccus: streptococcus aureus; G
-Bacillus: intestinal bacteria, Pseudomonas aeruginosa.
Get 13 sterilizing test tubes that the 1.0ml nutrient broth is housed and number respectively 1,2,3 ... ..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 liquid and makes the positive control pipe.From manage 12 pipes, draw 1.0 mixed solutions 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, the above-mentioned developmental tube of respectively organizing is put in 30～35 ℃ of incubators and cultivated 16～24h, 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, with the coating of aseptic L rod evenly, each concentration inoculation 3～4 flat board, culture put in 37 ℃ of thermostat containers cultivate, behind 24 h, not having colony growth is minimum sterilization dense (MBC).
Fungi: 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 sterilization dense (MFC).The result shows: silver, chitosan and derivates nanometer mixture pulvis sample thereof are to gram-positive microorganism (its representative strain is streptococcus aureus) and Gram-negative bacteria (its representative strain is enterobacteria, Pseudomonas aeruginosa), and fungi (its representative strain is Candida albicans) all has good germicidal action, and the result is as shown in table 2.Streptococcus aureus, intestinal bacteria, Pseudomonas aeruginosa, Candida albicans are surgery, skin, and gynecological infection (such as vaginitis, cervicitis, cervical erosion, bedsore, skin ulcer, burn, scald, wound, skin inflammation, tinea manus and pedis) common pathogen kind.
Table 2: sample bacteriostatic action research (sample Ag concentration: μ g/ml)
Then should be pointed out that with embodiment be the more representational example of the present invention, obvious technical scheme of the present invention is not limited to above-described embodiment.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 (2)
1. the preparation method of a silver, chitosan and/or chitosan derivatives nano-complex is characterized in that, adopts the liquid phase synthesizing method preparation, and step is as follows:
(1) with chitosan and/or chitosan derivatives is water-soluble or weakly 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 soln;
(3) under vigorous stirring, the silver nitrate aqueous solution or the silver-colored ammonia soln that dropwise slowly add step (2) gained in step (1) the gained solution, the part by weight of chitosan and/or chitosan derivatives and Silver Nitrate is 100:0.005～0.3, 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, namely get silver, chitosan and/or chitosan derivatives nano-complex that silver granuel directly is 1～100nm;
Described chitosan derivatives is one or several in hydroxypropyl chitosan, Hydroxypropyl chitosan, cm-chitosan, carboxymethyl chitin, succinyl-chitosan, the succinyl-chitin,
Described light source is tungsten-iodine lamp light, ultraviolet light or natural light.
2. preparation method according to claim 1 is characterized in that, the described organic solvent of step (4) is ethanol.
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