CN104128602A - Nano-silver antibacterial composite decorated by modified chitosan, preparing method and application - Google Patents
Nano-silver antibacterial composite decorated by modified chitosan, preparing method and application Download PDFInfo
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- CN104128602A CN104128602A CN201410381892.4A CN201410381892A CN104128602A CN 104128602 A CN104128602 A CN 104128602A CN 201410381892 A CN201410381892 A CN 201410381892A CN 104128602 A CN104128602 A CN 104128602A
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Abstract
The invention discloses a nano-silver antibacterial composite modified by modified chitosan and a preparing method of the nano-silver antibacterial composite. According to the nano-silver antibacterial composite and the preparing method of the nano-silver antibacterial composite, the chitosan with the small molecule quantiy and good water solubility is selected and used as a raw material, chemical modification is conducted on the chitosan by using small molecules which are capable of having chelation with nano-silver particles, the modified chitosan is arranged on the surfaces of the nano-silver particles in a covalent modification mode, and the novel nano-silver antibacterial composite is prepared. The prepared nano-silver antibacterial composite modified by the modified chitosan has good water solubility and dispersibility and can be stably dispersed in a water solution in a long term without aggregation under the conditions of high salinity and wide pH. The prepared nano-silver antibacterial composite modified by the modified chitosan enables the antibacterial property of the chitosan and the antibacterial property of nano-silver to be in effective synergy, the antibacterial performance is good, and the nano-silver antibacterial composite can serve as a water coating agent to perform the surface antibacterial function on the surfaces of materials and can also permeate into fiber type materials to perform the deep internal antibacterial function.
Description
Technical field
The invention belongs to nano-antibacterial composite material preparing technical field, be specifically related to nanometer silver antimicrobial composite of a kind of modification of chitosan modification and preparation method thereof.
Background technology
Polymer base inorganic nano-composite material is a kind of new material that inorganic nano material and Polymers are compounded to form, this material gets up the function synergic of polymer and inorganic nano material, show the total characteristic of inorganic nano material and polymer, be with a wide range of applications in many important technologies field.In antibacterial field, Nano Silver is widely used because it has potent antibacterial and effect broad-spectrum antiseptic.Its Antibacterial Mechanism is: Nano Silver by the silver ion that discharges the phosphide on bacterial cell membrane and sulfide be combined and destroy cell permeability of the membrane, entering after cell membrane and can continuation react with sulfide or phosphide on intracellular protein and DNA, function and the copying of DNA of blocking-up desmoenzyme are transcribed, thereby play antibacterial action.But the as easy as rolling off a log reunion of the Nano silver solution that does not pass through any modification, and Nano Silver is as a kind of metal nano material, it is not fine to biomembranous penetrability effect, uses separately Nano Silver to be difficult to enter and in bacterial cell, brings into play antibacterial action.Above defect has all limited the application of Nano Silver in antibacterial field.
Shitosan is a kind of eco-friendly natural macromolecular material, has good biocompatibility and degradability, contains a large amount of amino groups in its molecule.The antibiotic property of shitosan derives from amino protonated in its molecular structure.Amino on shitosan also can be for material is carried out to modification, thereby give material certain antibiotic property.But while using separately shitosan as antiseptic, under neutrality or slight alkali environment, due to the minimizing of protonated amino, chitosan anti-bacteria can weaken greatly.Therefore the composite of preparing shitosan and Nano Silver becomes a kind of desirable selection, and this composite can overcome the deficiency of shitosan anti-microbial property under neutrality or alkali condition, again can stabilized nanoscale silver particle.The people such as Zhang Yufei (stability of chitosan nano silver solution and the application on antibiotic finish of the fabric, high chemical journal, 2012,33,1860-1865) taking sodium borohydride as reducing agent, shitosan is stabilizing agent, has prepared chitosan nano silver solution, and has investigated stability and the antibiotic property of Nano Silver in system.But this composite be only simply rely on shitosan amino compound with the weak interaction of nano-Ag particles, in addition shitosan still can not, for Nano Silver provides enough hydrophily and stability, also can cause the gathering of chitosan nano silver composite material under the condition of neutrality or meta-alkalescence in the aqueous solution of high salinity.Therefore the stability of above-mentioned chitosan nano silver composite material is not good, thereby has limited the application of this material in antibacterial field.In order to address this problem, select the better shitosan raw material of hydrophily and stability, and to Chemical Modifying of Chitosan, make it covalent modification and form nano composite material on nano silver particles surface, become a kind of necessary choice.(the Preparation of Nanometer Silver In-Situ Reduction by Absorption of Crown Ether Crosslinked Chitosan such as Zhao Ting, Chinese leather, 2006,35,26-29) use crown ether cross-linked chitosan to do adsorbent and stabilizing agent, in aqueous medium, use hydrazine hydrate reduction silver nitrate to prepare a kind of composite nano anti-biotic material.By the Subjective and Objective effect of crown ether and silver ion, by shitosan covalent modification on Nano Silver surface.But still there is defect in this nano composite material: very loaded down with trivial details by the synthesis technique of Modified with Crown Ether modification of chitosan on the one hand, need four steps synthetic, in each step, all introduce a large amount of toxic organic solvent and intermediate product needs purification processes, cost is higher; Because the chitosan molecule amount of selecting is higher, the chitosan nano silver composite material stability of preparation is not good enough on the other hand, under meta-alkalescence condition, easily reunites, and antibacterial effect is limited, and can only be confined to as finishing agent in the antibacterial use of material surface.
Summary of the invention
One of object of the present invention is the problem existing for prior art, the nanometer silver antimicrobial composite that provides a kind of modification of chitosan can within the scope of high salinity and wide pH value with good antibacterial action to modify.
The nanometer silver antimicrobial composite that modification of chitosan of the present invention is modified, that top layer is the composite of shitosan, the internal layer nucleocapsid structure that is Nano Silver, described modification of chitosan is by carrying out the little molecule of function of chelation with nano silver particles and shitosan obtains by chemical graft, and percent grafting is 5% ~ 50%.
It is primary raw material that the present invention selects low-molecular-weight and water-soluble good shitosan, utilizes to contain the little molecule of function that can carry out chelating with Nano Silver shitosan is carried out to chemical modification, gives shitosan certain functional.Shitosan after this modification can covalency be sequestered in the surface of nano silver particles, prepares the nanometer silver antimicrobial composite that a kind of novel modification of chitosan is modified.This antimicrobial composite material can organically be worked in coordination with the antibacterial ability of shitosan and Nano Silver, has higher anti-microbial property.In addition, the good aqueous solubility that low-molecular weight chitoglycan has, can provide good stability of solution for Nano Silver, make antimicrobial composite material still can keep good stability and dispersiveness under high salinity and wide pH value value condition, thereby expanded the nano silver composite antibacterial material of modification of chitosan modification in the application in antibacterial field.This antimicrobial composite material not only can be used as aqueous coating agent in the effect of material surface performance antibacterial surface, can also be penetrated into performance deep inside antibacterial action in fiber-like material.
Described modification of chitosan is by carrying out the little molecule of function of chelation with nano silver particles and shitosan obtains by chemical graft, percent grafting is 5% ~ 50%, can prepare the nano silver composite material of surperficial different modifying density by the micromolecular percent grafting of regulatory function; The micromolecular percent grafting of function is lower, and more highdensity shitosan can be modified in Nano Silver surface, and the hydrophily of Nano Silver and stability also can increase, but corresponding cost also can increase.The shitosan density that can regulate Nano Silver surface to modify according to different antibacterial applications.
Preferably, described modification of chitosan is made by following methods: shitosan is fully dissolved in water, make the aqueous solution that chitosan concentration is 0.02 mol/L, to the little molecule of function that adds amino of chitosan molal quantity 5% ~ 50% in chitosan aqueous solution, and with 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) of the molal quantitys such as the little molecule of function and N-hydroxy-succinamide (NHS) as catalyst; At 30-80 DEG C, catalytic reaction 4-24h is grafted to little function molecule on shitosan, prepares the modification of chitosan aqueous solution, obtains the shitosan of chemical modification after dialysis freeze-drying; The little molecule of described function be one end with carboxyl, one end is the little molecule of function that can carry out with Nano Silver chelation in addition, preferably the following little molecule of several functions:
（1）
（2）
（3）
（4）
（5）
Wherein m=1 ~ 10.
Preferably, in step (1), the granularity of nano silver particles is 1nm ~ 100 nm; In step (2), the chitosan molecule amount in chitosan aqueous solution is 5000-50000, deacetylation >90%, and its chemical structural formula is as follows:
;
in formula, x is that 25 ~ 240, y is 25 ~ 240.
Can the size of nano particle smooth and easyly enter in bacterium and bring into play antibacterial action for it considerable influence.In the time that nano silver particles size is greater than 100nm, in Nano Silver bacterium more difficult to get access, anti-microbial property declines.
Preferably, described reducing agent is sodium borohydride, sodium thiosulfate or hydrogen peroxide.
Two of object of the present invention is to provide the method for the preparation nanometer silver antimicrobial composite that described modification of chitosan is modified, and comprises the steps:
(1) under 200-1000 rpm rotating speed stirring condition, be the reducing agent of 0.067 mol/L to adding 30 ml concentration during 10 ml concentration are the liquor argenti nitratis ophthalmicus of 0.1 mol/L, at 0-30 DEG C, react that within 2-10 hour, to prepare nano silver particles for subsequent use;
(2) shitosan is fully dissolved in water, make the aqueous solution that chitosan concentration is 0.02 mol/L, to the little molecule of function that adds amino of chitosan molal quantity 5% ~ 50% in chitosan aqueous solution, and with 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) of the molal quantitys such as the little molecule of function and N-hydroxy-succinamide (NHS) as catalyst; At 30-80 DEG C, catalytic reaction 4-24h is grafted to little function molecule on shitosan, prepares the modification of chitosan aqueous solution, obtains the shitosan of chemical modification after dialysis freeze-drying; The little molecule of described function be one end with carboxyl, one end is the little molecule of function that can carry out with Nano Silver chelation in addition, preferably the following little molecule of several functions:
（1）
（2）
（3）
（4）
（5）
Wherein m=1 ~ 10.
(3) in the gained modification of chitosan aqueous solution, add the nano silver particles by step (1) gained, under normal temperature, after stirring reaction 0.5-2 h, obtain the nanometer silver antimicrobial composite that modification of chitosan is modified.Preferably, described reducing agent is sodium borohydride, sodium thiosulfate or hydrogen peroxide.
Three of object of the present invention is to provide the method for the another kind of preparation nanometer silver antimicrobial composite that described modification of chitosan is modified, and comprises the steps:
(1) shitosan is fully dissolved in water, make the aqueous solution that chitosan concentration is 0.02 mol/L, to the little molecule of function that adds amino of chitosan molal quantity 5% ~ 50% in chitosan aqueous solution, and with 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) of the molal quantitys such as the little molecule of function and N-hydroxy-succinamide (NHS) as catalyst; At 30-80 DEG C, catalytic reaction 4-24h is grafted to little function molecule on shitosan, prepares the modification of chitosan aqueous solution, obtains the shitosan of chemical modification after dialysis freeze-drying; The little molecule of described function be one end with carboxyl, one end is the little molecule of function that can carry out with Nano Silver chelation in addition, preferably the following little molecule of several functions:
（1）
（2）
（3）
（4）
（5）
Wherein m=1 ~ 10.
(2) in the gained modification of chitosan aqueous solution, at 0-30 DEG C, drip liquor argenti nitratis ophthalmicus, add 0.2-100 that silver nitrate molal quantity is the little molecule molal quantity of institute's grafting functional on shitosan doubly, be uniformly mixed, then add and the reducing agent of the molal quantity such as silver nitrate, after in-situ reducing, make the nanometer silver antimicrobial composite that modification of chitosan is modified.
Preferably, in step (2), the granularity of nano silver particles is 1nm ~ 100 nm; In step (1), before modification, the molecular weight of shitosan is 5000-50000, deacetylation >90%, and its chemical structural formula is as follows:
In formula, x is that 25 ~ 240, y is 25 ~ 240.
Preferably, described reducing agent is sodium borohydride, sodium thiosulfate or hydrogen peroxide.
For preparation method of the present invention, described chitosan molecule amount is 5000 ~ 50000, and deacetylation >90%, has good aqueous solubility, environmental friendliness, raw material cheapness, wide material sources.On shitosan main chain, contain abundant amino, easily carry out number of chemical modification.
In Nano Silver preparation process, reaction temperature, silver nitrate concentration and reductant concentration have considerable influence to the size of prepared Nano Silver.In the time of the rising of reaction temperature, reduction reaction is accelerated, and has accelerated Brownian movement, and the reunion probability between Nano Silver is increased, thereby has increased the size of prepared Nano Silver; When liquor argenti nitratis ophthalmicus is in the time that finite concentration scope increases, the speed of crystal growing is greater than the speed of crystal nucleation, the size of gained Nano Silver can increase, but in the time that the concentration of liquor argenti nitratis ophthalmicus is excessive, the silver atoms that reaction generates can generate new nucleus, in nucleation process, will consume a large amount of simple substance silver, and cause required simple substance silver in nucleus growth process to reduce, and also can make gained nano silver particles size reduce; When the concentration of reducing agent increases, reaction is accelerated, and nano silver particles size is increased.Reaction temperature is set as to 0-30 DEG C, and silver nitrate concentration is 0.1 mol/L, and reductant concentration is 0.067 mol/L, and the reaction time is 2-10 hour, can make below 100nm and finely dispersed nano silver particles.Shitosan being carried out in the process of modification, 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS) play carboxyl on the little molecule of mobilizing function so that the effect of reacting with the amino on shitosan.When 1-(3-dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) and N-hydroxy-succinamide (NHS) molal quantity and the function small molecular phase while of containing carboxyl, can obtain the modification of chitosan of desired grafting amount.
Another object of the present invention is to provide the nanometer silver antimicrobial composite of described modification of chitosan modification in the application in antibacterial field.This composite can be used as aqueous coating agent in the effect of material surface performance antibacterial surface, can also be penetrated into performance deep inside antibacterial action in fiber-like material.
The present invention compared with the prior art, has following significant advantage:
1. raw material sources are extensive, cheap, and preparation technology is simple, reaction condition gentleness, and modifying process carries out in the aqueous solution, and only introduces a small amount of ethanol machine solvent, and toxicity is little, and environmental pollution is few;
Products obtained therefrom have good water-soluble, and can stable dispersion in high salinity and wide pH value environment, anti-microbial property excellence, can be in the industrial circle application of complicated condition;
3. products obtained therefrom can be worked in coordination with the antibiotic property of shitosan and Nano Silver efficiently, anti-microbial property is good, not only can be used as aqueous coating agent in the effect of material surface performance antibacterial surface, can also be penetrated into performance deep inside antibacterial action in fiber-like material.
The present invention prepares the nanometer silver antimicrobial composite that described modification of chitosan is modified, and both can adopt two-step method, can adopt again one-step method.When two-step method, first utilize reducing process to prepare nano-Ag particles, then be modified at Nano Silver surface with modification of chitosan, the advantage of two-step method is that modification of chitosan can modify the nano-Ag particles of different-grain diameter, and the Nano Silver particle diameter after modification distributes smaller.
When one-step method, be to be that modification of chitosan directly mixes with silver nitrate, utilize amino and the dispersed silver nitrate of hydroxyl on modification of chitosan, then add reducing agent in-situ reducing Nano Silver, shitosan also simultaneously covalent modification on Nano Silver surface.
Two kinds of techniques are all very simple, with low cost, and reaction condition is not harsh, are convenient to carry out industrialized production in enormous quantities.
Brief description of the drawings
Fig. 1 is low-molecular weight chitoglycan raw material (Chitosan in embodiment 1, CS), the infrared spectrum of the material such as the shitosan (CS-LA) after lipoic acid raw material (Lipoic Acid, LA), lipoic acid graft modification and the modification of chitosan Nano Silver (CS-LAAgNP) after modifying;
Fig. 2 is the TEM figure of the Nano Silver after modification of chitosan modification in embodiment 1, embodies good dispersiveness;
Fig. 3 is the TEM figure that does not pass through the Nano Silver of any modification in embodiment 1, does not have the Nano Silver of modification unstable, easily flocks together;
Fig. 4 is the UV absorption spectrogram of Nano Silver under condition of different pH that in embodiment 1, modification of chitosan is modified, and under wide pH value value, the characteristic absorption peak of Nano Silver does not change, and embodies good stability;
Fig. 5 is the UV absorption spectrogram of Nano Silver in the high salt concentration aqueous solution that in embodiment 1, modification of chitosan is modified, and in the high salt concentration aqueous solution, the characteristic absorption peak of Nano Silver does not change, and embodies good anti-salt-stable;
Fig. 6 is the nano silver material preparation technology schematic diagram that in embodiment 1, modification of chitosan is modified.
Fig. 7 is the antibacterial photo in application examples 1, and left figure is for not covering with paint, lacquer, colour wash, etc. chitosan nano parchment covering sample, and right figure is for having covered with paint, lacquer, colour wash, etc. chitosan nano parchment covering sample, and result shows that the skin sample of having covered with paint, lacquer, colour wash, etc. chitosan nano silver has good antibacterial effect.
detailed description of the invention:
Embodiment 1
(1) preparation of modification of chitosan CS-LA
Shitosan is fully dissolved in water, makes the aqueous solution that chitosan concentration is 0.02 mol/L; The lipoic acid that takes amino of chitosan molal quantity 5%, is dissolved in ethanol, then adds the carboxyl that activates lipoic acid with the EDC of lipoic acid equimolar amounts and NHS, adds in chitosan solution after mixing, reacts 4h at 30 DEG C; Reaction finishes rear dialysis and removes unreacted lipoic acid and EDC/NHS activator, obtains modification of chitosan product C S-LA after reactant liquor freeze drying, and chemical structural formula is as follows:
Shitosan after modification contains disulfide bond group, can be used for covalent modification Nano Silver.
(2) preparation of Nano Silver
Be that in the liquor argenti nitratis ophthalmicus of 0.1 mol/L, to add 30 ml concentration be the borane reducing agent sodium hydride of 0.067 mol/L to 10 ml concentration, taking the natrium citricum of 1mmol as stabilizing agent, under the mixing speed of lucifuge condition and 1000rpm, reaction 2 h, obtain the stable nano silver particles of natrium citricum.The stable Nano Silver of natrium citricum is unstable, easily assembles after depositing certain hour.
(3) modification of chitosan decorated nanometer silver
Modification of chitosan CS-LA is directly joined in the nano silver particles in step (2), normal-temperature reaction 0.5 h, CS-LA can replace natrium citricum gradually, thereby covalent modification is to Nano Silver surface, obtains the nano silver composite material (CS-LAAg NP) that modification of chitosan is modified after dialysis.
Embodiment 2
(1) preparation of modification of chitosan CS-LA
Shitosan is fully dissolved in water, makes the aqueous solution that chitosan concentration is 0.02 mol/L; The lipoic acid that takes amino of chitosan molal quantity 50%, is dissolved in ethanol, then adds the carboxyl that activates lipoic acid with the EDC of lipoic acid equimolar amounts and NHS, adds in chitosan solution after mixing, reacts 24h at 80 DEG C; Reaction finishes rear dialysis and removes unreacted lipoic acid and EDC/NHS activator, obtains and modification of chitosan product C S-LA that in embodiment 1, step (1) is identical after reactant liquor freeze drying;
(2) modification of chitosan CS-LA is dissolved in the aqueous solution, in above-mentioned solution, drip liquor argenti nitratis ophthalmicus, add 0.2 times for institute's grafting lipoic acid molal quantity on shitosan of silver nitrate molal quantity, utilize amino on shitosan and hydroxyl stable and disperse silver nitrate, then add the borane reducing agent sodium hydride with molal quantitys such as silver nitrates, at 0 DEG C, it is Nano Silver that lucifuge stirs in-situ reducing after a period of time, and finishing shitosan (CS-LAAg NP);
The Nano Silver technique that one-step method in-situ reducing modification of chitosan is modified is simple, has reduced cost, is conducive to industrialized mass.
Embodiment 3
(1) preparation of gallic acid modification of chitosan CS-GA
Shitosan is fully dissolved in water, makes the aqueous solution that chitosan concentration is 0.02 mol/L; The gallic acid that takes amino of chitosan molal quantity 25 %, is dissolved in ethanol, then adds the carboxyl that activates gallic acid with the EDC of gallic acid equimolar amounts and NHS, adds in chitosan solution after mixing, reacts 24 h at 50 DEG C; Reaction finishes rear dialysis and removes unreacted gallic acid and EDC/NHS activator, obtains modification of chitosan product C S-GA after reactant liquor freeze drying, and chemical structural formula is as follows:
(2) preparation of Nano Silver
Be that in the liquor argenti nitratis ophthalmicus of 0.1 mol/L, to add 30 ml concentration be the reducing agent sodium thiosulfate of 0.067 mol/L to 10 ml concentration, taking the natrium citricum of 1mmol as stabilizing agent, under the mixing speed of lucifuge condition and 200rpm, react 10 h, obtain the stable nano silver particles of natrium citricum.The stable Nano Silver of natrium citricum is unstable, easily assembles after depositing certain hour.
(3) modification of chitosan decorated nanometer silver
Modification of chitosan CS-GA is directly joined in the nano silver particles in step (2), normal-temperature reaction 2 h, CS-GA can replace natrium citricum gradually, utilize the phenolic hydroxyl group of gallic acid to be chelated to Nano Silver surface, after dialysis, obtain the nano silver composite material (CS-GAAg NP) that modification of chitosan is modified.
Embodiment 4
(1) preparation of modification of chitosan CS-GA
Preparation process is as step (1) in embodiment 3, and obtains same products;
(2) modification of chitosan CS-LA is dissolved in the aqueous solution, in above-mentioned solution, drip liquor argenti nitratis ophthalmicus, add 100 times for institute's grafting gallic acid molal quantity on shitosan of silver nitrate molal quantity, utilize the fixing silver ion of phenolic hydroxyl group original position of gallic acid on shitosan, then add the reducing agent sodium thiosulfate with molal quantitys such as silver nitrates, at 30 DEG C, it is Nano Silver that lucifuge stirs in-situ reducing after a period of time, and finishing shitosan;
The phenolic hydroxyl group of gallic acid not only can chelating Nano silver grain, also can chelated silver iron, be more suitable for in-situ reducing, and gallic acid itself just there is certain reproducibility, and can very easyly obtain the Nano Silver (CS-LAAg NP) that modification of chitosan is modified.
Embodiment 5
(1) preparation of mercaptopropionic acid modification of chitosan CS-TA
Shitosan is fully dissolved in water, makes the aqueous solution that chitosan concentration is 0.02 mol/L; The mercaptopropionic acid that takes amino of chitosan molal quantity 10 %, is dissolved in ethanol, then adds the carboxyl that activates mercaptopropionic acid with the EDC of mercaptopropionic acid equimolar amounts and NHS, adds in chitosan solution after mixing, reacts 20 h at 60 DEG C; Reaction finishes rear dialysis and removes unreacted mercaptopropionic acid and EDC/NHS activator, obtains modification of chitosan product C S-TA after reactant liquor freeze drying, and chemical structural formula is as follows:
(2) preparation of Nano Silver
Be that in the liquor argenti nitratis ophthalmicus of 0.1 mol/L, to add 30 ml concentration be the reducing agent hydrogen peroxide of 0.067 mol/L to 10 ml concentration, taking the natrium citricum of 1mmol as stabilizing agent, under the mixing speed of lucifuge condition and 500rpm, react 5 h, obtain the stable nano silver particles of natrium citricum.The stable Nano Silver of natrium citricum is unstable, easily assembles after depositing certain hour.
(3) modification of chitosan decorated nanometer silver
Modification of chitosan CS-GA is directly joined in the nano silver particles in step (2), normal-temperature reaction 1 h, CS-GA can replace natrium citricum gradually, utilizes sulfydryl to be chelated to Nano Silver surface, obtains the nano silver composite material (CS-TAAg NP) that modification of chitosan is modified after dialysis.
Embodiment 6
(1) preparation of modification of chitosan CS-TA
Preparation process is as step (1) in embodiment 5, and obtains same products;
(2) modification of chitosan CS-LA is dissolved in the aqueous solution, in above-mentioned solution, drip liquor argenti nitratis ophthalmicus, add 50 times for institute's grafting gallic acid molal quantity on shitosan of silver nitrate molal quantity, utilize amino and the hydroxyl dispersion on shitosan and stablize silver nitrate ion, then add the reducing agent hydrogen peroxide with molal quantitys such as silver nitrates, at 15 DEG C, it is Nano Silver that lucifuge stirs in-situ reducing after a period of time, and finishing shitosan (CS-TAAg NP).
application examples 1
Leather surface antibacterial applications:
(1) blue wet pigskin shaving-rinsing-retanning-neutralization-stuffing (selecting the lecithin fatting agent of easy mildew)-washing-extension dries in the air;
(2) skin sample is cut into the circular skin graft that diameter is 2 about cm, then under uviol lamp to skin graft two sides sterilization treatment;
(3) skin graft after sterilizing is immersed in the chitosan nano silver composite material aqueous solution in embodiment 1, and concussion 30 min, take out post-drying;
(4), in the agar medium that surface dip-coating has the skin graft of chitosan nano silver anti-biotic material to be positioned over to contain penicillium chrysogenum (common mould in wet blue), cultivate and carry out inhibition zone mensuration after 5 days.
In contrast to the crown ether cross-linked chitosan nano silver composite antibacterial agent of people's reports such as Zhao Ting, under the concentration of 10 mg/l of shitosan lipoic acid nano silver antimicrobials, inhibition zone reaches 20 mm, be equivalent to the effect of crown ether cross-linked chitosan nano silver composite antibacterial agent under 300 mg/l, antibacterial ability promotes 30 times.
application examples 2
Leather degree of depth antibacterial applications:
(1) to put into concentration be in the 10 mg/l chitosan nano silver aqueous solution to the wet pigskin of the indigo plant after chrome tanning, rotates 30 min in rotary drum, and chitosan nano silver particulate is fully filled between materials with hide glue fibril.Leather after filling is used glutaraldehyde retanning again, by glutaraldehyde, chitosan nano silver is fixed on collagen;
(2) the pigskin leather should use-case making is compared with the pigskin leather of common process, and the physical and mechanical properties of dermatotome improves, and richness increases, flexibility indifference;
(3) add that the pigskin of Nano Silver dries, be cut into skin graft after sterilizing, skin graft is positioned in the agar medium that contains penicillium chrysogenum (common mould in wet blue), cultivates and carries out inhibition zone mensuration after 5 days; More than its inhibition zone all reaches 20 mm, observe and find in 10 days, chitosan nano silver has lasting antibacterial ability in leather.
Claims (10)
1. the nanometer silver antimicrobial composite that modification of chitosan is modified, it is characterized in that: be that top layer is the composite of shitosan, the internal layer nucleocapsid structure that is Nano Silver, described modification of chitosan is by carrying out the little molecule of function of chelation with nano silver particles and shitosan obtains by chemical graft, and percent grafting is 5% ~ 50%.
2. the nanometer silver antimicrobial composite that modification of chitosan according to claim 1 is modified, is characterized in that: described modification of chitosan is made by following methods:
Shitosan is fully dissolved in water, make the aqueous solution that chitosan concentration is 0.02 mol/L, add the little molecule of function of amino of chitosan molal quantity 5% ~ 50% to chitosan aqueous solution, and with 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) of the molal quantitys such as the little molecule of function and N-hydroxy-succinamide (NHS) as catalyst; At 30-80 DEG C, catalytic reaction 4-24h is grafted to little function molecule on shitosan, prepares the modification of chitosan aqueous solution, obtains the shitosan of chemical modification after dialysis freeze-drying; The little molecule of described function be one end with carboxyl, one end is the little molecule of function that can carry out with Nano Silver chelation in addition, preferably the following little molecule of several functions:
（1）
（2）
（3）
（4）
（5）
Wherein m=1 ~ 10.
3. the nanometer silver antimicrobial composite that modification of chitosan according to claim 1 and 2 is modified, it is characterized in that, in chitosan aqueous solution, the deacetylation >90% of shitosan used, molecular weight is 5000-50000, and its chemical structural formula is as follows:
；
In formula, x is that 25 ~ 240, y is 25 ~ 240.
4. the nanometer silver antimicrobial composite that modification of chitosan according to claim 3 is modified, is characterized in that, described nano silver particles is prepared by reducing process, and granularity is 1nm ~ 100 nm.
5. the method for the nanometer silver antimicrobial composite that the described modification of chitosan of preparation is modified, is characterized in that, comprises the steps:
(1) under 200-1000 rpm rotating speed stirring condition, be the reducing agent of 0.067 mol/L to adding 30 ml concentration during 10 ml concentration are the liquor argenti nitratis ophthalmicus of 0.1 mol/L, taking the natrium citricum of 1mmol as stabilizing agent, at 0-30 DEG C, react that within 2-10 hour, to prepare nano silver particles for subsequent use;
(2) shitosan is fully dissolved in water, make the aqueous solution that chitosan concentration is 0.02 mol/L, to the little molecule of function that adds amino of chitosan molal quantity 5% ~ 50% in chitosan aqueous solution, and with 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) of the molal quantitys such as the little molecule of function and N-hydroxy-succinamide (NHS) as catalyst; At 30-80 DEG C, catalytic reaction 4-24h is grafted to little function molecule on shitosan, prepares the modification of chitosan aqueous solution, obtains the shitosan of chemical modification after dialysis freeze-drying; The little molecule of described function be one end with carboxyl, one end is the little molecule of function that can carry out with Nano Silver chelation in addition, preferably the following little molecule of several functions:
（1）
（2）
（3）
（4）
（5）
Wherein m=1 ~ 10;
(3) in the gained modification of chitosan aqueous solution, add the nano silver particles by step (1) gained, under normal temperature, after stirring reaction 0.5-2 h, obtain the nanometer silver antimicrobial composite that modification of chitosan is modified.
6. the method for the nanometer silver antimicrobial composite of preparing modification of chitosan modification according to claim 5, is characterized in that: in step (1), the granularity of nano silver particles is 1nm ~ 100 nm; In step (2), the chitosan molecule amount in chitosan aqueous solution is 5000-50000, deacetylation >90%, and its chemical structural formula is as follows:
In formula, x is that 25 ~ 240, y is 25 ~ 240.
7. according to the method for the nanometer silver antimicrobial composite of preparing modification of chitosan modification described in right 5 or 6, it is characterized in that: described reducing agent is sodium borohydride, sodium thiosulfate or hydrogen peroxide.
8. the method for the nanometer silver antimicrobial composite that the described modification of chitosan of preparation is modified, is characterized in that, comprises the steps:
(1) shitosan is fully dissolved in water, make the aqueous solution that chitosan concentration is 0.02 mol/L, to the little molecule of function that adds amino of chitosan molal quantity 5% ~ 50% in chitosan aqueous solution, and with 1-(3-the dimethylamino-propyl)-3-ethyl-carbodiimide hydrochloride (EDC) of the molal quantitys such as the little molecule of function and N-hydroxy-succinamide (NHS) as catalyst; At 30-80 DEG C, catalytic reaction 4-24h is grafted to little function molecule on shitosan, prepares the modification of chitosan aqueous solution, obtains the shitosan of chemical modification after dialysis freeze-drying; The little molecule of described function be one end with carboxyl, one end is the little molecule of function that can carry out with Nano Silver chelation in addition, preferably the following little molecule of several functions:
（1）
（2）
（3）
（4）
（5）
Wherein m=1 ~ 10;
(2) in the gained modification of chitosan aqueous solution, at 0-30 DEG C, drip liquor argenti nitratis ophthalmicus, add 0.2-100 that silver nitrate molal quantity is the little molecule molal quantity of institute's grafting functional on shitosan doubly, be uniformly mixed, then add and the reducing agent of the molal quantity such as silver nitrate, after in-situ reducing, make the nanometer silver antimicrobial composite that modification of chitosan is modified.
9. the method for the nanometer silver antimicrobial composite of preparing modification of chitosan modification according to claim 8, is characterized in that, in step (2), the granularity of nano silver particles is 1nm ~ 100 nm; In step (1), before modification chitosan molecule amount be 5000-50000, deacetylation >90%, its chemical structural formula is as follows:
In formula, x is that 25 ~ 240, y is 25 ~ 240; Described reducing agent is sodium borohydride, sodium thiosulfate or hydrogen peroxide.
10. the nanometer silver antimicrobial composite of modifying according to modification of chitosan described in claim 1-9 is in the application in antibacterial field.
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