CN104145993B - A kind of chitosan and silver-bearing copper are blended the method preparing complex antimicrobials - Google Patents
A kind of chitosan and silver-bearing copper are blended the method preparing complex antimicrobials Download PDFInfo
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- CN104145993B CN104145993B CN201410379214.4A CN201410379214A CN104145993B CN 104145993 B CN104145993 B CN 104145993B CN 201410379214 A CN201410379214 A CN 201410379214A CN 104145993 B CN104145993 B CN 104145993B
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Abstract
A kind of chitosan and silver-bearing copper are blended the method preparing complex antimicrobials, its described method be the concentration by silver nitrate and copper nitrate than mixing for 1:30 1:80 after, then with chitosan blend.Prepare light blue anti-bacterial powders.The method reduces the usage amount of silver, wherein chitosan serves as reducing agent and uses, it is to avoid adds chemical reagent, reduces the toxicity of antibacterial.This is because the change of process conditions so that chitosan is fully carried out with the redox reaction of copper nitrate, has the generation of aldehyde radical (CHO) in the reaction so that Ag+It is completely reduced into elemental silver, Cu2+Live in seclusion in chitosan basal body, thus play synergetic antibacterial effect, through the detection of antibacterial ring test, escherichia coli and golden yellow glucose coccus there is inhibitory action significantly, >=antibacterial the ring of 10mm is defined under the condition of culture of 37 DEG C, there is bacteriostasis significantly, material therefor is harmless, cheap, is the NEW TYPE OF COMPOSITE antibacterial of a kind of environmental protection.
Description
Technical field
The present invention relates to the preparation method of a kind of complex antimicrobials, a kind of employing chitosan for weaving and silver
The preparation method of the complex antimicrobials that copper is blended.
Background technology
Existing preparation has the antibacterial of the chitosan class of anti-microbial property and generally all uses Ag to exist as main antibacterial.
Chitosan is a large amount of a kind of natural green alkaline polysaccharides existed in biosphere, has substantial amounts of hydroxyl and amino etc. to live
Property group, it is easy to metal ion is stung conjunction.And there is the biocompatibility of uniqueness, biological degradability, antibiotic property, avirulence, life
Thing activity and physicochemical properties cause the attention of people, chemical industry, weave, print and dye, papermaking and medicine and other fields have widely
Application prospect.
" preparation method of a kind of silver-loaded silica-chitosan compound anti-bacteria agent " of Publication No. CN 101297654
Patent of invention, this patent is with silicon dioxide as inorganic raw material, with polymer chitosan as Organic Ingredients, with deionized water, nitre
Acid silver, ammonia, KH-550, glacial acetic acid, dilute hydrochloric acid, glutaraldehyde, dehydrated alcohol are reagent, by water-soluble synthesis chemical reaction,
Obtain white powder eventually.This method technological process is short, uses equipment few.But this patent uses more acid in preparation process
Class chemical reagent, i.e. increases cost, also makes to be restricted in medical material application aspect, easily produces health and threatens.
The Hu Zongzhi of SanXia University, the good grade of forest of Zhongshan University has been inquired into natural polymer chitosan as raw material, with
Polyvinyl alcohol carries out solution blending and it is carried out toughening modifying, and in this blend film, chitosan has between the two with polyvinyl alcohol
The well compatibility, toughness has obtained obvious improvement, but its heat stability has declined with hot strength, the most not body
Reveal the anti-microbial property that chitosan is had.
The Wei Liqiao of Institutes Of Technology Of Taiyuan has inquired into the composite antibacterial latex of chitosan-loaded silver, and this invention gathers with polymer shell
Sugar is Organic Ingredients, with deionized water, silver nitrate, sodium borohydride, dehydrated alcohol etc. as reagent, anti-by water-soluble synthesis chemistry
Should, finally giving the antibacterial latex of brown, this method technological process is short, uses equipment few.But this patent is in preparation process
Employ the reagent such as borane reducing agent sodium hydride, this is because chitosan is weak reductant, it is impossible to be elemental silver by silver nitrate reduction,
And the silver nitrate amount that preparation process uses is relatively greatly, adds the cost of commercial Application.
Summary of the invention
The present invention uses chitosan as the mantle plate of antibacterial, is blended by silver-bearing copper and obtains a kind of complex antimicrobials so that it is
There is good and safe anti-microbial property.Addition copper, to solve in existing product silver-colored usage amount, is not required in preparation process
Want the chemical reagent such as additional reducing agent, obtain that anti-microbial property is good and the green NEW TYPE OF COMPOSITE antibacterial of low cost, thus provide one
Plant chitosan and be blended, with silver-bearing copper, the method preparing complex antimicrobials.
Above-mentioned purpose is achieved through the following technical solutions.
A kind of chitosan and silver-bearing copper are blended the method preparing complex antimicrobials, and its described method is to follow these steps to carry out
:
(1) it is the ratio of 1:1-1:5 in concentration than for 1:30-1:80, volume ratio with copper nitrate solution by silver nitrate solution
Add agitator；
(2) agitator is slowly heated up, and control temperature 35 DEG C-45 DEG C stir 1h, control temperature stir at 52 DEG C-58 DEG C
Mix 1h；Rear standing half an hour；
(3) again it is warmed up to 60 DEG C-68 DEG C, adds 0.5g chitosan, after generating light blue suspension after stirring 0.5 h,
Stand；
(4) until suspension cool down after in circulating vacuum pump sucking filtration, obtain light blue powder, put it into 60 DEG C be dried
Case is dried；
(5) dried powder is ground, i.e. obtains the complex antimicrobials powder that chitosan is blended with silver-bearing copper.
Wherein, described silver nitrate and copper nitrate solution are 1:50 by concentration than further；It is 1:3 the most further；
Described silver nitrate is elemental silver after being reduced.
Technique scheme is on the basis of the project research of this seminar, according to chemical reaction mechanism, further investigated
Silver nitrate, copper nitrate and chitosan are in liquid and liquid, solid-state and solid-state, in the reaction of uniform temperature between liquid and solid-state
Process, uses reverse thinking, through lot of experiments, uses and is first mixed in proportion with copper nitrate solution by silver nitrate solution,
Then adding solid chitosan to react, achieve unforeseeable effect, its unforeseeable effect is:
This method uses chitosan as the mantle plate of antibacterial, silver and copper is blended and obtains a kind of complex antimicrobials, makes
It has long-acting lasting, safe anti-microbial property.Addition copper is to solve to silver-colored usage amount in existing product, in preparation process
Need not the chemical reagent such as additional reducing agent, obtain anti-microbial property good, and the green NEW TYPE OF COMPOSITE antibacterial of low cost, the present invention
The main technological features of the preparation method of the complex antimicrobials that chitosan is blended with silver-bearing copper is:
(1) antibacterial prepared by forefathers is all first to add chitosan to prepare antibacterial latex, and the present invention is by this preparation
Method is inverted, and finally adds chitosan and prepares the antibacterial of powder, and its antibacterial effect is more preferably.
(2) the heated and stirred method gradually heated up is used with copper nitrate solution when silver nitrate solution is blended so that it is solution
Mix is more preferably uniform, and beneficially chitosan does not produce agglomeration after adding.
(3) chitosan added is pressed powder rather than chitosan solution, and the powder antibacterial so generated ratio is anti-
The anti-microbial property of bacterium colloidal sol is more excellent.
The complex antimicrobials that chitosan prepared by this method is blended with silver-bearing copper detects through antibacterial ring test: to escherichia coli
With staphylococcus aureus, there is significant bacteriostasis, under the condition of culture of 37 DEG C, define >=antibacterial the ring of 10mm, as
Accompanying drawing 4 and accompanying drawing 5；Chitosan and silver-bearing copper be blended after good than chitosan and silver of heat stability so that its application is more
Extensively；And this method is easy and simple to handle, fast, eliminate the use of toxic chemical, ensure the health of the person, can be safely
For medical domain and textile industry, and material price is cheap, economical and practical, for manufacturing natural stabilisation, harmless biology
Medical macromolecular materials provide a kind of new way.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of chitosan of the present invention and silver-bearing copper complex antimicrobials.By scheming clearly visible chitosan outward appearance
Compact structure, in bulk sheet, and also exists some granular materials uniformly, and creates on the matrix of chitosan
The lamellar structure that multilamellar covers, is more beneficial for the attachment of metal grain so that play antibacterial work in the antibacterial of equal quality
Antibacterial increase.
Fig. 2 is chitosan of the present invention and the infrared spectrogram of silver complex antimicrobials.Figure is seen 3429 cm-1The strong peak at place
Belong to CTS intramolecular amino (-NH2) and the stretching vibration absworption peak of light base (-0H), 1556 cm-1The characteristic absorption peak occurred
The characteristic peak of corresponding nanometer silver.
Fig. 3 is the infrared spectrogram of chitosan of the present invention and silver-bearing copper complex antimicrobials.Figure being seen, CTS/Ag/Cu is antibacterial multiple
The position of the absworption peak that compound is overall does not the most change, and characteristic absorption peak still exists, but at 3429 cm-1、2974 cm-1、2934 cm-1、1631 cm-1 、1396 cm-1、1085cm-1、1046 cm-1、885 cm-1Locate corresponding absorption peak strength
Weaken, at 1425 cm-1、1320cm-1The stretching vibration absworption peak of the C-N at place disappears, and explanation is more-NH on CTS2With
Ag+There occurs complexation reaction；Meanwhile, 1087 cm-1With 1025 cm-1Corresponding secondary alcohol and the C-0 stretching vibration of primary alconol absorb
Peak is the most unchanged, and not raw with the silver hair complexation reaction of light base of the primary and secondary alcohol of CTS is described.
Fig. 4 is the colibacillary antibacterial ring test figure of chitosan of the present invention and silver-bearing copper complex antimicrobials.Figure is seen:
Overgrow with around blank sample colibacillary bacterium colony, chitosan and silver-bearing copper be blended complex antimicrobials around then define >=
The antibacterial ring of 10mm, it was demonstrated that this antibacterial has anti-microbial property.
Fig. 5 is the antibacterial ring test of the staphylococcus aureus of the complex antimicrobials that chitosan of the present invention is blended with silver-bearing copper
Figure.Figure is seen the bacterium colony overgrowing with staphylococcus aureus around blank sample, and being combined that chitosan and silver-bearing copper are blended is anti-
>=antibacterial the ring of 10mm is then defined, it was demonstrated that this antibacterial has anti-microbial property around microbial inoculum.
Detailed description of the invention
The preparation method of the complex antimicrobials that chitosan of the present invention and silver-bearing copper are blended is by nitre by its composition and content proportioning
Acid silver and copper nitrate are made into blend solution for 1:3 by volume and stir in agitator, to be mixed uniform after add chitosan, molten
Liquid becomes light blue suspension, the suspension after cooling carries out sucking filtration, dry, grinding, finally gives light blue powder shape
Complex antimicrobials.
The detailed description of the invention of the present invention is further described below by specific embodiment.
Embodiment 1
(1) being dissolved in 25ml deionized water by 0.004g silver nitrate, 0.94g copper nitrate is dissolved in 100ml deionized water,
Its concentration, than for 1:50, mixes for 1:3 by volume；
(2) solution of mixing is placed in thermostatic mixer, at 40 DEG C, stirs 1h under the rotating speed of 25r/min, by temperature
It is raised to 50 DEG C, under the rotating speed of 25r/min, is stirred for 1h；
(3) temperature is raised to 60 DEG C, under the rotating speed of 25r/min, adds 0.5g chitosan solid stirring 0.5h, generate light
Blue suspension；
(4) after cooling, suspension is carried out sucking filtration, in 60 DEG C of calorstats, is dried complete, grinding, i.e. obtain pale blue toner
The complex antimicrobials of powder.
Obtain being made up of chitosan and silver nitrate and copper nitrate by above-mentioned preparation method, be nitric acid by its content proportioning
Silver is 1:50 with the ratio of the concentration of copper nitrate, and the ratio of volume is 1:3, generates the complex antimicrobials that chitosan is blended with silver-bearing copper.
Embodiment 2
According to the process of embodiment 1, the difference of embodiment 2 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio becomes 1:2, generates the complex antimicrobials that chitosan is blended with silver-bearing copper.Understand through bacteriostasis circle test, antibacterial
Ring diameter is 8 mm, and its fungistatic effect can not show a candle to embodiment 1.
Embodiment 3
According to the process of embodiment 1, the difference of embodiment 3 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio becomes 1:1, generates the complex antimicrobials that chitosan is blended with silver-bearing copper.Understand through bacteriostasis circle test, antibacterial
Ring diameter is 7 mm, and its fungistatic effect can not show a candle to embodiment 1.
Embodiment 4
According to the process of embodiment 1, the difference of embodiment 4 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio is 1:3.It is raised to 60 DEG C in temperature, under the rotating speed of 25r/min, adds the stirring of 0.5g chitosan solution
0.5h, generates the complex antimicrobials that light blue colloidal sol is blended.Understanding through bacteriostasis circle test, inhibition zone diameter is 6 mm, without antibacterial
Property.
Embodiment 5
According to the process of embodiment 1, the difference of embodiment 5 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio is 1:3.In thermostatic mixer, at constant temperature 60 DEG C, stir 2h, temperature constant after solution mixing, generate shell
The complex antimicrobials that polysaccharide is blended with silver-bearing copper.Understanding through bacteriostasis circle test, inhibition zone diameter is 11 mm, its fungistatic effect and reality
As executing example 1, but cost is high, and power consumption is big.
Embodiment 6
According to the process of embodiment 1, the difference of embodiment 6 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:40, its volume ratio becomes 1:3, generates the complex antimicrobials that chitosan is blended with silver-bearing copper.Understand through bacteriostasis circle test, antibacterial
Ring diameter is 8 mm, and its fungistatic effect can not show a candle to embodiment 1.
Embodiment 7
According to the process of embodiment 1, the difference of embodiment 7 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio is 1:3.It is raised to 60 DEG C in temperature, under the rotating speed of 25r/min, adds the stirring of 0.5g chitosan solution
0.5h, gradually drips sodium borohydride solution, generates the blend of black suspension.Understand through bacteriostasis circle test, inhibition zone diameter
Being 6 mm, without antibiotic property, and antibacterial color is also a drawback.
Embodiment 8
According to the process of embodiment 1, the difference of embodiment 8 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio is 1:3.0.5g chitosan is dissolved in 25ml deionized water in thermostatic mixer 60 DEG C, 25r/min
Rotating speed under stir, be simultaneously introduced silver nitrate and copper nitrate mixed solution, form colloidal sol blend.Continue stirring 2h, generate shell
The complex antimicrobials that polysaccharide is blended with silver-bearing copper.Understanding through bacteriostasis circle test, inhibition zone diameter is 7 mm, and its fungistatic effect is remote not
Such as embodiment 1.
Embodiment 9
According to the process of embodiment 1, the difference of embodiment 9 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio is 1:3.0.5g chitosan is dissolved in 25ml deionized water in thermostatic mixer 60 DEG C, 25r/min
Rotating speed under stir, be simultaneously introduced silver nitrate and copper nitrate mixed solution, form colloidal sol blend.Continuation stirring 2h, more gradually
Dropping sodium borohydride solution, generates yellowish-brown colloidal sol blend.Understanding through bacteriostasis circle test, inhibition zone diameter is 9 mm, and it presses down
Bacterium effect is not so good as embodiment 1.
Embodiment 10
According to the process of embodiment 1, the difference of embodiment 10 is: silver nitrate and the concentration proportioning of copper nitrate solution
For 1:50, its volume ratio is 1:3.The blue suspension generated is dried after carrying out sucking filtration in atmosphere, can become black powder
Blend.Understanding through bacteriostasis circle test, inhibition zone diameter is 5 mm, and its fungistatic effect can not show a candle to embodiment 1.
Claims (1)
1. chitosan and silver-bearing copper are blended the method preparing complex antimicrobials, and its described method follows these steps to carry out:
(1) being dissolved in 25ml deionized water by 0.004g silver nitrate, 0.94g copper nitrate is dissolved in 100ml deionized water, by body
Long-pending ratio mixes for 1:3；
(2) solution of mixing is placed in thermostatic mixer, at 40 DEG C, stirs 1h under the rotating speed of 25r/min, temperature is raised to
50 DEG C, under the rotating speed of 25r/min, it is stirred for 1h；
(3) temperature is raised to 60 DEG C, under the rotating speed of 25r/min, adds 0.5g chitosan solid stirring 0.5h, generate light blue
Suspension；
(4) after cooling, suspension is carried out sucking filtration, in 60 DEG C of calorstats, is dried complete, grinding, i.e. obtain light blue powder shape
Complex antimicrobials.
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