CN106751920B - Preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver and products thereof and application - Google Patents
Preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver and products thereof and application Download PDFInfo
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Abstract
The present invention relates to preparation methods of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver and products thereof and application, specific method is that silk gum is extracted from silk cocoon, then it is configured to silk gum solution, poly-vinyl alcohol solution is added into silk gum solution again, it is uniformly mixed, drying obtains polyvinyl alcohol-silk gum laminated film after freeze-thaw recycles；Then polyvinyl alcohol-silk gum laminated film is sequentially placed into polyacrylic acid solution, polydimethyl diallyl ammonium chloride solution and polyacrylic acid solution and is impregnated, polyvinyl alcohol-silk gum the laminated film for obtaining polyelectrolyte layer package, finally obtains the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver with ultraviolet irradiation reduction method.This method enables nano silver be modified securely on polyvinyl alcohol-silk gum laminated film surface, and is uniformly distributed, and makes it have the antibacterial activity of long duration；And preparation process is simple, and it is low in cost, it is expected to be applied to biomedical anti-biotic material related fields.
Description
Technical field
The invention belongs to biomedical anti-biotic material fields, and in particular to polyvinyl alcohol-silk gum-nano silver is enhanced compound
The preparation method of film anti-biotic material further relates to the application of product obtained by this method He the product.
Background technique
Fibroin is mainly made of fibroin albumen and sericin.Wherein the 20-30% of the total cocoon weight of silk gum Zhan, fibroin account for
The 70-80% of total cocoon weight, fibroin are widely used in textile industry and medical field.However, for a long time, silk gum is de- in silk
It is taken as waste in glue treatment process and abandons.The silk gum being lost every year in the world is up to 500000 tons, and silk gum is being degraded
Need to consume a large amount of oxygen in the process, therefore the discharge of silk gum undoubtedly will cause serious environmental pollution.If this day of silk gum
Right bioprotein can be developed and used reasonably, not only can produce great economic benefit, but also can reduce to ring
The pollution in border.Silk gum is made of multiple polypeptides, contains 18 kinds of amino acid, includes some of needed by human body in this 18 kinds of amino acid
It must amino acid.Wherein three kinds of most amino acid serines of content, aspartic acid and glutamic acid have corresponding pharmacological use.
Serine can prevent and treat hypertension, synthesis treatment tuberculosis and anti-tumor drug.Glycine can reduce cholesterol, blood in blood
The content of sugar has good effect for prevention and treatment hypertension and diabetes.Asparatate has protective effect to liver and cardiac muscle,
It can be used for treating the diseases such as angina pectoris, myocardial infarction.In addition, sericin have good bioactivity, as inoxidizability,
Promote proliferation and the differentiation etc. of cell, in addition to this, silk gum also has biodegradability, good hydrophily, and possesses
Polar group abundant, therefore regenerative medicine field is received more and more attention and is applied to, but silk gum itself is some
Defect is for example frangible etc. to limit its application.Blending is generallyd use at present, is grafted the method for macromolecule polyalcohol to silk gum progress
It is modified, to widen sericin in the application of different field.
With the development of science and technology, nanotechnology is receive more and more attention.It is varied to have different structure and function
The nano material of energy is prepared out, and is widely used in different fields.Nano silver series anti-biotic material is a kind of extensive
The nano anti-biotic material of application, with large specific surface area, surface reaction activity is high, Active sites are more, high catalytic efficiency, suction
The features such as attached ability is strong.Nano silver antibacterial material has the antibacterial activity of wide spectrum, for Gram-negative bacteria and Gram-positive
Bacterium all has good resistance, and have it is heat-resist, highly-safe, be not likely to produce the advantages such as drug resistance, but actually answering
In, nano silver is easy to fall off, and is affected to some extent so as to cause its long-term antibacterial activity.And by nano silver and silk gum egg
The white performance combined while improving sericin and nano silver has not been reported.
Summary of the invention
In view of this, one of the objects of the present invention is to provide a kind of polyvinyl alcohol-enhanced THIN COMPOSITEs of silk gum-nano silver
The preparation method of film anti-biotic material；The second object of the present invention is to provide product obtained by this method；The purpose of the present invention
Three be that providing the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver is preparing the application in anti-biotic material.
In order to achieve the above objectives, the invention provides the following technical scheme:
The preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver, includes the following steps:
(1) preparation of silk gum powder: taking silk cocoon to carry out degumming, collects silk gum solution, then that silk gum freezing solution is laggard
Row freeze-drying, obtains silk gum powder；
(2) polyvinyl alcohol-silk gum laminated film preparation: silk gum powder is made in step (1) and is dissolved in water, it is molten to obtain silk gum
Liquid；Then silk gum solution is blended with poly-vinyl alcohol solution, recycles to obtain silk gum-polyvinyl alcohol Compound Water by freeze-thaw
Gel dries to obtain polyvinyl alcohol-silk gum laminated film；
(3) polyvinyl alcohol of polyelectrolyte layer package-silk gum laminated film preparation: by polyvinyl alcohol-silk obtained by step (2)
Glue laminated film is first soaked in polyacrylic acid solution, obtains the negatively charged polyvinyl alcohol in surface-silk gum laminated film；Then
It is soaked in dimethyl diallyl ammonium chloride solution, then impregnated with polyacrylic acid solution, is dried after final rinse water, obtained poly-
Polyvinyl alcohol-silk gum laminated film of electrolyte layer package；
(4) polyvinyl alcohol of nanometer modified by silver-silk gum laminated film anti-biotic material preparation: by poly- electricity obtained by step (3)
Polyvinyl alcohol-silk gum laminated film of solution matter layer package is placed in AgNO3It is poly- in silk gum-using ultraviolet irradiation reduction method in solution
The surface synthesizing nano-silver of vinyl alcohol blend film obtains the enhanced laminated film antibacterial material of polyvinyl alcohol-silk gum-nano silver
Material.
In the present invention, step (1) is that silk cocoon is taken to shred, and bath raio is that 1:30 adds water, the degumming under the conditions of 120 DEG C, 0.1Mpa
20~30min；Then by freeze-drying after freezing at -80 DEG C, silk gum powder is obtained.
In step (2) of the present invention, the concentration of the silk gum solution is 4% (w/t)；The poly-vinyl alcohol solution concentration is
5% (wt)；Freeze-thaw circulation is freezed 4 hours under the conditions of -20 DEG C, thaws 1 under the conditions of being then put in 18-25 DEG C
It~2 hours, recycles 4 times；The temperature of the drying is 55 DEG C.
Preferably, the mass ratio of the silk gum solution and poly-vinyl alcohol solution is 3:3.
In the present invention, step (3) is 2% for polyvinyl alcohol-silk gum laminated film obtained by step (2) is first soaked in concentration
(w/v) 2~8min in polyacrylic acid solution obtains the negatively charged polyvinyl alcohol in surface-silk gum laminated film；Then impregnate
In concentration be 2% (w/v) dimethyl diallyl ammonium chloride solution in 2~8min, then with concentration be 2% (w/v) poly- third
Olefin(e) acid solution impregnates 2~8min, dries after finally being rinsed with deionized water, obtains polyvinyl alcohol-silk gum of polyelectrolyte layer package
Laminated film.
In the present invention, step (4) is by polyvinyl alcohol-silk gum laminated film of the package of polyelectrolyte layer obtained by step (3)
Being placed in concentration is 20mM AgNO3In solution, it is enhanced multiple to obtain polyvinyl alcohol-silk gum-nano silver by ultraviolet irradiation at least 10min
Close film anti-biotic material.
2, the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver as made from the preparation method.
3, the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver is preparing answering in anti-biotic material
With.
Preferably, the anti-biotic material is resisting gram-positive bacteria or/and Gram-negative bacteria material.
It is furthermore preferred that the resisting gram-positive bacteria is Escherichia coli, the Gram-negative bacteria is Staphylococcus aureus
Bacterium.
The beneficial effects of the present invention are: it is anti-that the invention discloses polyvinyl alcohol-enhanced laminated films of silk gum-nano silver
The preparation method of bacterium material is successfully prepared using after the sericin and polyvinyl alcohol blending extracted in silk cocoon with good
The polyvinyl alcohol of good mechanical property-silk gum laminated film；Then by electrostatic adsorption in polyvinyl alcohol-silk gum laminated film
Area load charged polymeric nitride layer recycles ultraviolet reduction method in polyvinyl alcohol-silk gum laminated film surface finish nano silver, mentions
The high load capacity of nano silver, and it is secured in laminated film surface modification to make nano silver, to obtain a kind of there is durable antibiotic
The active enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver.The experimental method letter of this self-assembled film
It is single, it is easy to repeat；Polymer passes through strong electrostatic interactions between layers and is combined together, and improves polyelectrolyte
The stability of membrane structure；It is applied widely.Theoretically, any molecule with opposite charges can be by this method from group
Dress forms polyelectrolyte layer, and this method has stronger practicability.In the poly- electricity of polyvinyl alcohol-silk gum laminated film pan coating
Matter layer is solved, the load capacity of silver nanoparticle ion not only can be improved, but also silver nanoparticle ion can be enhanced by electrostatic adsorption
And the combination of polyelectrolyte layer, to impart the long-acting enduringly antibacterial activity of polyvinyl alcohol-silk gum laminated film.Film tool
There is the anti-microbial property of good mechanical performance, biocompatibility, water imbibition and high-efficient and lasting, can be used for the related doctor such as antiseptic dressing
With technical field of biological material, have a good application prospect.
Detailed description of the invention
In order to keep the purpose of the present invention, technical scheme and beneficial effects clearer, the present invention provides following attached drawing and carries out
Illustrate:
Fig. 1 is the preparation principle schematic diagram of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver.
Fig. 2 is that the surface Scanning Electron microscope of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver shines
Piece (A: polyvinyl alcohol-silk gum laminated film of polyelectrolyte layer package；B: laminated film is placed in 20mM AgNO3It is ultraviolet in solution
Irradiate 10min；C: the compound silk gum film of polyelectrolyte layer package is placed in 20mM AgNO3Ultraviolet irradiation 10min in solution；D:
The compound silk gum film of polyelectrolyte layer package is placed in 20mM AgNO3Ultraviolet irradiation 30min in solution).
Fig. 3 is the XRD spectrum of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver.
Fig. 4 is the FT-IR map (a: silk gum of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver；B:
Polyvinyl alcohol-silk gum laminated film；C: the laminated film of polyelectrolyte layer package；D: the polyelectrolyte layer package of nanometer modified by silver
Laminated film).
Fig. 5 is Escherichia coli and golden yellow after the addition enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver
Staphylococcic growth curve (A: the growth curve of Escherichia coli；B: the growth curve of staphylococcus aureus).
Fig. 6 is Escherichia coli and golden yellow after the addition enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver
(A is the antibacterial ring size figure of Escherichia coli to staphylococcic antibacterial ring size；B is the antibacterial ring size figure of staphylococcus aureus).
Specific embodiment
Below in conjunction with attached drawing, a preferred embodiment of the present invention will be described in detail.
The enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver, schematic diagram is as shown in Figure 1, be specifically logical
The method for crossing high temperature and pressure extracts sericin from silkworm silk cocoon, and poly-vinyl alcohol solution then is added in silk gum solution, mixes
It closes uniformly, drying obtains polyvinyl alcohol-silk gum laminated film after freeze-thaw recycles；Then pass through electrostatic interaction
Polyelectrolyte layer is wrapped up on laminated film surface, positively charged silver ion is adsorbed on to the table of laminated film using Electrostatic Absorption
Face, then with the method that ultraviolet irradiation restores by nanometer modified by silver on laminated film surface, and then obtain polyvinyl alcohol-silk gum-
The enhanced laminated film anti-biotic material of nano silver.The film have good mechanical performance, biocompatibility, water imbibition and efficiently
Lasting anti-microbial property can be used for the related biomaterial for medical purpose such as antiseptic dressing field.
Embodiment 1
The preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver, includes the following steps:
(1) preparation of silk gum powder: weighing the silk cocoon of constant weight, shred, according to 1:30 bath raio 121 DEG C,
High temperature and pressure 30min under conditions of 0.1MPa obtains silk gum solution through filtration treatment, then silk gum solution is placed in -80 DEG C of item
4h is freezed under part, is then freeze-dried, and silk gum powder is obtained；
(2) polyvinyl alcohol-silk gum laminated film preparation: silk gum powder obtained by step (1) is molten for 4% (wt) by concentration
In hot water (90 DEG C), then it is 5% (wt) that obtained silk gum solution is 3:3 addition concentration into silk gum solution in mass ratio
Poly-vinyl alcohol solution after being put in -20 DEG C of freezing 4h, room temperature (18~25 DEG C) defrosting 1h is put in, by 4 times after mixing
After freeze-thaw circulation, the composite hydrogel of forming is taken out, obtains polyvinyl alcohol-silk gum laminated film after 55 DEG C of drying；
(3) polyvinyl alcohol of polyelectrolyte layer package-silk gum laminated film preparation: by polyvinyl alcohol-silk obtained by step (2)
Glue laminated film is soaked in 2min in 2% (w/v, g/ml) polyacrylic acid solution (PAA), is subsequently placed in 2% (w/v, g/ml's)
2min is impregnated in dimethyl diallyl ammonium chloride (PDDA) solution, then is placed in 2% (w/v, g/ml) polyacrylic acid solution (PAA)
Middle immersion 2min, deionized water are rinsed, and the laminated film of polyelectrolyte layer package is obtained after drying, and wherein polyelectrolyte layer is
PAA-PDDA-PAA。
(4) polyvinyl alcohol of nanometer modified by silver-silk gum laminated film anti-biotic material preparation: by poly- electricity obtained by step (3)
Polyvinyl alcohol-silk gum laminated film of solution matter package is put into the AgNO of 20mM3In solution, after ultraviolet irradiation 10min, it will receive
Rice modified by silver obtains the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver on the surface of laminated film.
Embodiment 2
The preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver, includes the following steps:
(1) preparation of silk gum powder: weighing the silk cocoon of constant weight, shred, according to 1:30 bath raio 121 DEG C,
High temperature and pressure 30min under conditions of 0.1MPa obtains silk gum solution through filtration treatment, then silk gum solution is placed in -80 DEG C of item
4h is freezed under part, is then freeze-dried, and silk gum powder is obtained；
(2) polyvinyl alcohol-silk gum laminated film preparation: silk gum powder obtained by step (1) is molten for 4% (wt) by concentration
In hot water (90 DEG C), then it is 5% (wt) that obtained silk gum solution is 3:3 addition concentration into silk gum solution in mass ratio
Poly-vinyl alcohol solution after being put in -20 DEG C of freezing 4h, room temperature (18~25 DEG C) defrosting 1h is put in, by 4 times after mixing
After freeze-thaw circulation, the composite hydrogel of forming is taken out, obtains polyvinyl alcohol-silk gum laminated film after 55 DEG C of drying；
(3) polyvinyl alcohol of polyelectrolyte layer package-silk gum laminated film preparation: by polyvinyl alcohol-silk obtained by step (2)
Glue laminated film is soaked in 4min in 2% (w/v, g/ml) polyacrylic acid solution (PAA), is subsequently placed in 2% (w/v, g/ml's)
4min is impregnated in dimethyl diallyl ammonium chloride (PDDA) solution, then is placed in 2% (w/v, g/ml) polyacrylic acid solution (PAA)
Middle immersion 4min, deionized water are rinsed, and the laminated film of polyelectrolyte layer package is obtained after drying, and wherein polyelectrolyte layer is
PAA-PDDA-PAA。
(4) polyvinyl alcohol of nanometer modified by silver-silk gum laminated film anti-biotic material preparation: by poly- electricity obtained by step (3)
Polyvinyl alcohol-silk gum laminated film of solution matter package is put into the AgNO of 20mM3In solution, after ultraviolet irradiation 10min, it will receive
Rice modified by silver obtains the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver on the surface of laminated film.
Embodiment 3
The preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver, includes the following steps:
(1) preparation of silk gum powder: weighing the silk cocoon of constant weight, shred, according to 1:30 bath raio 121 DEG C,
High temperature and pressure 30min under conditions of 0.1MPa obtains silk gum solution through filtration treatment, then silk gum solution is placed in -80 DEG C of item
4h is freezed under part, is then freeze-dried, and silk gum powder is obtained；
(2) polyvinyl alcohol-silk gum laminated film preparation: silk gum powder obtained by step (1) is molten for 4% (wt) by concentration
In hot water (90 DEG C), obtain silk gum solution, be then in mass ratio into silk gum solution 3:3 be added concentration be 5% (wt)
Poly-vinyl alcohol solution after being put in -20 DEG C of freezing 4h, is put in room temperature (18~25 DEG C) defrosting 1h after mixing, cold by 4 times
After jelly-thaw cycles, the composite hydrogel of forming is taken out, obtains polyvinyl alcohol-silk gum laminated film after 55 DEG C of drying；
(3) polyvinyl alcohol of polyelectrolyte layer package-silk gum laminated film preparation: by polyvinyl alcohol-silk obtained by step (2)
Glue laminated film is soaked in 8min in 2% (w/v, g/ml) polyacrylic acid solution (PAA), is subsequently placed in 2% (w/v, g/ml's)
8min is impregnated in dimethyl diallyl ammonium chloride (PDDA) solution, then is placed in 2% (w/v, g/ml) polyacrylic acid solution (PAA)
Middle immersion 8min, deionized water are rinsed, and the laminated film of polyelectrolyte layer package is obtained after drying, and wherein polyelectrolyte layer is
PAA-PDDA-PAA。
(4) polyvinyl alcohol of nanometer modified by silver-silk gum laminated film anti-biotic material preparation: by poly- electricity obtained by step (3)
Polyvinyl alcohol-silk gum laminated film of solution matter package is put into the AgNO of 20mM3In solution, after ultraviolet irradiation 10min, it will receive
Rice modified by silver obtains the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver on the surface of laminated film.
Embodiment 4, characterization test
The enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver made from Examples 1 to 3 is carried out related
Characterization test, specific as follows:
(1) scanning electron microscope (SEM) is tested: each fritter of film that respectively prepared by Example 1~3 is placed in patch
On the objective table of conducting resinl, metal spraying processing is carried out, in 10kV voltage, amplifies 1300 times, under the technical parameters such as high vacuum mode, institute
The surface sweeping sem image obtained is as shown in Figure 2.The results show that the polyvinyl alcohol of polyelectrolyte layer package-silk gum is enhanced THIN COMPOSITE
Film is soaked in 20mM AgNO3In solution, after ultraviolet irradiation can surface finish nano silver, and nanometer modified by silver amount with
The increase of time of ultraviolet irradiation and the laminated film that increases, and do not wrap up polyelectrolyte layer be only capable of modifying a small amount of nano silver, table
The bright load capacity that can be improved nano silver particles in polyvinyl alcohol-silk gum enhancing laminated film surface package polyelectrolyte layer.
(2) X-ray diffraction (XRD) is tested: the film that respectively prepared by Example 1~3 carries out XRD diagram spectrum analysis, as a result
As shown in Figure 3.The result shows that nano silver is successfully modified in polyvinyl alcohol-silk gum laminated film surface of polyelectrolyte layer package.
(3) FT-IR map testing result is as shown in Figure 4.The results show that answering of wrapping up of the polyelectrolyte layer of nanometer modified by silver
Film is closed in 3274cm-1, 1640cm-1, 1531cm-1And 1248cm-1There is characteristic peak at place, shows the compound of polyelectrolyte layer package
Film surface successfully modifies nano silver.
(4) bacteriostatic experiment
1), growth curve is tested
The present embodiment passes through to the bacterium and addition polyvinyl alcohol-silk gum laminated film, polyelectrolyte layer packet grown naturally
The polyvinyl alcohol of the polyvinyl alcohol wrapped up in-silk gum laminated film or nanometer modified by silver-silk gum enhancing laminated film bacterial growth is bent
Line compares, so that it is determined that the polyvinyl alcohol of nanometer modified by silver-silk gum enhancing laminated film antibacterial effect, specific method
Are as follows:
1. Escherichia coli (E.coli) and the single colonie of staphylococcus aureus (S.aureus) is taken to be inoculated in sterilizing respectively
100mL LB liquid medium (pH 7.4) in, cultivated 12 hours under the conditions of revolving speed is 220rpm, temperature is 37 DEG C；
2. the Escherichia coli and 100 μ L of staphylococcus aureus bacteria suspension that take step (1) to activate respectively are added to 10mL LB
In culture medium, every kind of bacterium solution prepares 4 groups, wherein one group is blank group, remaining 3 groups are separately added into polyvinyl alcohol-silk gum THIN COMPOSITE
Polyvinyl alcohol-silk gum of film, polyvinyl alcohol-silk gum laminated film of polyelectrolyte layer package or nanometer modified by silver enhances THIN COMPOSITE
Then film is cultivated under the conditions of revolving speed is 220rpm, temperature is 37 DEG C, and 0h, 1h, 2h, 3h, 4h, 6h, 8h, 12h, 14h,
Bacteria suspension 0.5mL is taken when 18h, 22h, 26h and 30h, in 4 DEG C of Storage in refrigerator；
3. the bacteria suspension that different time takes out is taken out from 4 DEG C of refrigerators after the bacteria suspension sampling wait cultivate 30h, room temperature
Its absorbance value at 600nm of UV spectrophotometer measuring is utilized after placing 20-40min under (18-25 DEG C), according to measuring
Absorption value draw the growth curve of Escherichia coli and staphylococcus aureus respectively, as a result as shown in Figure 5.Analyze polyethylene
The polyvinyl alcohol-of alcohol-silk gum laminated film, polyvinyl alcohol-silk gum laminated film of polyelectrolyte layer package or nanometer modified by silver
Silk gum enhances influence of the laminated film to bacterial growth, the results show that the polyvinyl alcohol of addition nanometer modified by silver-silk gum enhancing is multiple
After closing film, the growth of Escherichia coli and staphylococcus aureus receives obvious inhibition, and the time is up to 22h or more, table
Polyvinyl alcohol-silk gum laminated film of bright nanometer modified by silver prepared by the present invention has excellent and lasting antibacterial activity.
2), Bactericidal test
For further determine that nanometer modified by silver compound silk gum film antibacterial action, tested using the method for inhibition zone
The polyvinyl alcohol of nanometer modified by silver-fungistatic effect of the silk gum enhancing laminated film to Escherichia coli and staphylococcus aureus, tool
Body method is as follows:
1. the single colonie of Escherichia coli and staphylococcus aureus is taken to be inoculated in the 100mL LB Liquid Culture of sterilizing respectively
In base (pH7.4), cultivated 10 hours under the conditions of revolving speed is 220rpm, temperature is 37 DEG C；
2. take 200~300 μ L that LB solid culture primary surface is added after the bacteria suspension of step (1) activation is diluted 100 times, and
It is cultivated 1-2 hours in the shaking table that revolving speed is 220rpm, dilution is made to be evenly distributed on agar media surface；
3. taking diameter is polyvinyl alcohol-silk gum of polyvinyl alcohol-silk gum laminated film of 1.5cm, polyelectrolyte layer package
The polyvinyl alcohol of laminated film or nanometer modified by silver-silk gum enhances laminated film, is laid in the LB culture that dilution is evenly distributed
Primary surface；Then 12h is cultivated under the conditions of 37 DEG C, as a result as shown in Figure 6.The results show that multiple being placed with polyvinyl alcohol-silk gum
In the LB culture medium for closing film, it is inoculated on the culture medium of Escherichia coli and the culture medium of inoculation staphylococcus aureus and is not formed
Apparent inhibition zone shows that polyvinyl alcohol-silk gum laminated film itself to the no inhibiting effect of the growth of Escherichia coli, is being placed
In polyvinyl alcohol-silk gum laminated film LB culture medium of polyelectrolyte layer package, apparent inhibition zone is not observed yet, is shown
Polyelectrolyte layer itself does not have much influence the growth of bacterium, and in the polyvinyl alcohol-silk gum for being placed with nanometer modified by silver
In the plate for enhancing laminated film, it can be observed that foring apparent inhibition zone, show polyvinyl alcohol-silk of nanometer modified by silver
Glue, which enhances laminated film, has significant bacteriostasis, the enhanced laminated film anti-biotic material tool of polyvinyl alcohol-silk gum-nano silver
There is excellent anti-microbial property.
Finally, it is stated that preferred embodiment above is only used to illustrate the technical scheme of the present invention and not to limit it, although logical
It crosses above preferred embodiment the present invention is described in detail, however, those skilled in the art should understand that, can be
Various changes are made to it in form and in details, without departing from claims of the present invention limited range.
Claims (7)
1. the preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver, which is characterized in that including such as
Lower step:
(1) preparation of silk gum powder: taking silk cocoon to carry out degumming, collects silk gum solution, then will carry out after silk gum freezing solution cold
It is lyophilized dry, obtains silk gum powder；
(2) polyvinyl alcohol-silk gum laminated film preparation: silk gum powder is made in step (1) and is dissolved in water, silk gum solution is obtained；
Then silk gum solution is blended with poly-vinyl alcohol solution, recycles to obtain silk gum-polyvinyl alcohol compound water congealing by freeze-thaw
Glue dries to obtain polyvinyl alcohol-silk gum laminated film；The concentration of the silk gum solution is 4%(wt)；The poly-vinyl alcohol solution is dense
Degree is 5%(wt)；The mass ratio of the silk gum solution and poly-vinyl alcohol solution is 3:3；The freeze-thaw circulation is at -20 DEG C
Under the conditions of freeze 4 hours, thaw 1 ~ 2 hour under the conditions of being then put in 18-25 DEG C, recycle 4 times；The temperature of the drying is 55
℃；
(3) polyvinyl alcohol of polyelectrolyte layer package-silk gum laminated film preparation: polyvinyl alcohol-silk gum obtained by step (2) is multiple
It closes film and is soaked in concentration first as 2 ~ 8min in the polyacrylic acid solution of 2%(w/v), obtain the negatively charged polyvinyl alcohol-in surface
Silk gum laminated film；Then being soaked in concentration is 2%(w/v) dimethyl diallyl ammonium chloride solution in 2 ~ 8min, then with dense
Degree impregnates 2 ~ 8min for the polyacrylic acid solution of 2%(w/v), dries after finally being rinsed with deionized water, obtains polyelectrolyte layer package
Polyvinyl alcohol-silk gum laminated film；
(4) polyvinyl alcohol of nanometer modified by silver-silk gum laminated film anti-biotic material preparation: by polyelectrolyte obtained by step (3)
Polyvinyl alcohol-silk gum laminated film of layer package is placed in AgNO3In solution, using ultraviolet irradiation reduction method in silk gum-polyethylene
The surface synthesizing nano-silver of alcohol blend film obtains the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver.
2. the preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver according to claim 1,
It is characterized by: step (1) is that silk cocoon is taken to shred, bath raio is that 1:30 adds water, the degumming 20 ~ 30 under the conditions of 120 DEG C, 0.1 Mpa
min；Then by freeze-drying after freezing at -80 DEG C, silk gum powder is obtained.
3. the preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver according to claim 1,
It is characterized by: step (4) is dense for polyvinyl alcohol-silk gum laminated film of the package of polyelectrolyte layer obtained by step (3) to be placed in
Degree is 20mM AgNO3In solution, it is anti-to obtain polyvinyl alcohol-silk gum-nanometer human lymph node laminated film by ultraviolet irradiation at least 10min
Bacterium material.
4. polyvinyl alcohol-silk gum-nanometer human lymph node laminated film as made from any one of claim 1 ~ 3 preparation method is anti-
Bacterium material.
5. polyvinyl alcohol-silk gum described in claim 4-nanometer human lymph node laminated film anti-biotic material is in preparing anti-biotic material
Using.
6. application according to claim 5, it is characterised in that: the anti-biotic material is resisting gram-positive bacteria or/and leather
Lan Shi negative bacterium material.
7. application according to claim 6, it is characterised in that: the resisting gram-positive bacteria is Escherichia coli, the leather
Lan Shi negative bacterium is staphylococcus aureus.
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| CN103834050A (en) * | 2014-03-21 | 2014-06-04 | 北京科技大学 | Method for preparing gelatin/nano-silver/chitosan derivative composite film |
| CN105854066A (en) * | 2016-04-14 | 2016-08-17 | 西南大学 | Method of modifying polyelectrolyte thin film coated sericin gel with nano-silver and product and application thereof |
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| JP2004217603A (en) * | 2003-01-17 | 2004-08-05 | Katayama Chem Works Co Ltd | Antibacterial paste composition and antibacterial treatment method |
| CN101200553A (en) * | 2006-12-14 | 2008-06-18 | 中国科学院理化技术研究所 | Slver particles/polyvinyl alcohol composite as well as preparation method and uses thereof |
| CN101028536A (en) * | 2007-03-02 | 2007-09-05 | 上海交通大学 | Production of polyvinyl alcohol/sericin blended gel thin film |
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