A kind of preparation method carrying silver-colored chitosan/polyvinyl alcohol micro belt
Technical field
The present invention relates to composite nano-fiber material field, in particular to a kind of load silver chitosan with anti-microbial property/
Polyvinyl alcohol micron band and the preparation method and application thereof.
Background technique
Noble silver is used as high-efficiency antimicrobial material because of its unique photoelectric characteristic, high chemical stability and catalytic activity
Material.Nano material has big specific surface area and high catalytic activity, has preferably catalysis and sterilization compared to its block materials
Etc. performances.In recent years, people prepare the Argent grain of nanoscale by various means, and this nano silver has superior antibacterial
Performance.But it is small-sized due to nano silver, when exclusive use, it is easy to be lost, therefore, generally will in practical application
It is carried on carrier material, to play its excellent sterilizing ability.By nano-silver loaded into nanofiber, it can utilize
The great specific surface area of nanofiber increases the contact area of nano silver and bacterium, and can be effectively prevented in use process silver-colored
Loss, it is more more efficient than many conventional methods.
The good life of design feature and chitosan material that one-dimensional chitosan-based material has large specific surface area, porosity high
Object medical performance is a kind of green fiber with good environmental-protecting performance.Since viscosity is higher in an acidic solution, band for chitosan
Positive charge and intramolecular and the effect of intermolecular strong chemical bond, cause it to be difficult to move freely during electrostatic spinning, cause
Fiber is discontinuous, is broken containing pearl or even spinning.And high-specific surface area, continuous flawless can be made in electrostatic blended spinning technology
Nanofiber, the tunica fibrosa than chitosan alone preparation is more tough and tensile durable, and cost of material is also lower.Polyvinyl alcohol 1788
(PVA) with the grease resistance and solvent resistance of good chemical stability and physical mechanical property and brilliance.Further, since
PVA has good biocompatibility and degradability, is widely applied frequently as biomimetic material.High-molecular polyvinyl alcohol passes through
Hydrogen bond action has more good electrostatic spinning performance in conjunction with chitosan, than other polymer.
Chinese patent document CN104511045A (application number: 201310441908.1) is disclosed a kind of containing nano silver
The preparation method of chitosan/polyvinyl alcohol nanofiber film dressing, the nanofiber film dressing are mixed with polyvinyl alcohol and chitosan
Conjunction object is substrate, by the way that silver sol is added dropwise, obtains chitosan/polyvinyl alcohol nano fibrous membrane using method of electrostatic spinning, then benefit
It is crosslinked to obtain water-resistance anti-bacterial fibre with glutaraldehyde and nano fibrous membrane.
Chinese patent document CN103705969A (application number: 201410001923.9) discloses a kind of chitosan base load silver
The preparation method of composite antibacterial type superfine fibre film, specific steps include: step 1: in the acetic acid that mass fraction is 50-90%
Silver nitrate powder is added in aqueous solution, stirs to dissolve, weighs chitosan and polyethylene glycol oxide or pva powder is added
Into above-mentioned solution, spinning solution is stirred to get;Step 2: electrostatic spinning apparatus is added in spinning solution, voltage be 10-20kV,
Spinning solution injects speed 0.1-1.0mL/h, reception distance is 8-30cm, spinning temperature is 20-50 DEG C and relative humidity is 10-
Electrostatic spinning is carried out under conditions of 55%, and obtained white nano fibrous membrane is dried in vacuo 12-36h, removes remaining solvent,
Obtain chitosan-based silver-loaded composite antimicrobial superfine fiber membrane.
But the absorption of tunica fibrosa specific surface area, porosity, imbibition rate, nano silver that above-mentioned two patent documents obtain
Ability and bacteriostasis property are all to be improved.
Monodimension nanometer material is received extensive attention due to its excellent physical and chemical performance, two-dimension nano materials due to
Stratiform and the characteristics such as controllable and furtherd investigate.The characteristics of micron carrying material has had both a peacekeeping two-dimension nano materials, is current
Forward position material in Nanometer scale science and technology research and development is relatively new knot between a peacekeeping two-dimensional nanostructure
Structure has rectangular section, and width-thickness ratio is bigger, there is unique property;This very thin strip nanostructure, neither
It is same as the hollow structure of nanotube, and the different solid cylinder structures with nano wire.Micro belt Material Manufacturing Process is easy to control,
Material structure can be made unified when mass production, internal structure is perfect, surface is clean smooth and does not have internal flaw, dislocation,
Purity is higher, these properties enable it to put into industrial production earlier.
Currently, directly preparing the silver-colored chitosan/polyvinyl alcohol micro belt of load using electrostatic spinning technique, relevant report is had no.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of silver-colored chitosan/polyvinyl alcohol micro belt of load and its preparations
Mixed liquor, polyvinyl alcohol is added using polyvinyl alcohol and chitosan compound as substrate, by silver nitrate in method and application, the micro belt
As reducing agent, chitosan prepares the chitosan/polyvinyl alcohol micro belt containing nano silver as stabilizer.
Technical scheme is as follows:
A kind of silver-colored chitosan/polyvinyl alcohol micro belt of load, the micro belt be evenly distributed with the chitosan of silver nano-grain/
The band-like composite cellulosic membrane of polyvinyl alcohol, micro belt diameter are 0.3-2 μm, and the partial size of silver nano-grain is 5-60nm.
, according to the invention it is preferred to, the micro belt is with a thickness of 100-300nm.
, according to the invention it is preferred to, described 0.5-1.5 μm of micro belt diameter, silver nano-grain partial size is 5-40nm.
According to the present invention, the preparation method of above-mentioned load silver chitosan/polyvinyl alcohol micro belt, comprises the following steps that
Ethyl alcohol is added after the lactic acid solution of poly-vinyl alcohol solution and chitosan is mixed, is stirring evenly and then adding into silver nitrate,
It is protected from light stirring 40-50h, is made into spinning solution, then electrostatic spinning obtains carrying silver-colored chitosan/polyvinyl alcohol micro belt.
Preparation method according to the present invention, it is preferred that the mass concentration of the poly-vinyl alcohol solution is 10-20%, institute
The lactic acid solution mass concentration for the chitosan stated is 2-8%;
Preferably, the mass ratio of poly-vinyl alcohol solution, the lactic acid solution of chitosan and ethyl alcohol is (90-70): (10-30):
(5-10)。
Preparation method according to the present invention, it is preferred that the additional amount of silver nitrate is the 2 of polyvinyl alcohol and chitosan gross mass
~8%.
Preparation method according to the present invention, it is preferred that the condition of electrostatic spinning are as follows:
It is received using aluminium foil, voltage 15-20kV, syringe pump fltting speed is 1.5-3mL/h, and receiving distance is 12-
18cm, temperature are 20-25 DEG C.
According to the present invention, above-mentioned load silver chitosan/polyvinyl alcohol micro belt is preparing the application in medical dressing.
Silver nitrate is added using chitosan as stabilizer using polyvinyl alcohol as the reducing agent of silver ion by the present invention
Into chitosan/polyvinyl alcohol mixed liquor, silver ion is made to be reduced into nano silver, the method preparation of this " from bottom to top " is received
The problems such as rice Argent grain diameter is smaller, avoids and is unevenly distributed after being directly added into nano-silver powder, and partial size is uneven.Using electrostatic spinning
Method can make nano silver once-forming with micro belt, and nano-Ag particles is allowed to adhere to or be embedded in chitosan/polyvinyl alcohol micro belt
In, it is effectively reduced phenomena such as falling off and reunite of nano silver, makes the distribution of the nano silver to be formed in micro belt more evenly.
Using the broad spectrum antibacterial of nano silver, micro belt prepared by the present invention can be used as medical dressing.Polyvinyl alcohol is water-soluble high score
Son can form a large amount of hydrogen bond containing a large amount of hydroxyl with hydrone, and therefore, compound micro belt prepared by the present invention can absorb
Moisture can provide the environment of wetting for wound.
Beneficial effects of the present invention:
1, the advantages of load silver chitosan/polyvinyl alcohol micro belt of the invention is with a peacekeeping two-dimension nano materials, both
It is different from solid nanofiber again different from nanotube, compared to existing nanofiber, micro belt, which possesses, higher compares table
Area, porosity and water absorption rate, nano-Ag particles adhere to or are embedded in chitosan/polyvinyl alcohol micro belt, due to bandwidth
Than relatively thin, avoid excessive nano silver and be embedded in inside, be effectively reduced phenomena such as falling off and reunite of nano silver, make shape
At distribution of the nano silver in micro belt more evenly.
2, load silver chitosan/polyvinyl alcohol micro belt preparation process of the invention is simpler, using polyvinyl alcohol as
Reducing agent, chitosan is as stabilizer, and in-situ reducing is at nano silver.And selected substrate is all degradability and biocompatibility
Green material, improve the pattern of film, prepare the chitosan/polyvinyl alcohol micro belt of argentiferous, with broad spectrum antibacterial
Feature, the lethality to Escherichia coli are 100%.
Detailed description of the invention
Fig. 1 is that the ultra-violet absorption spectrum for being protected from light stirring different time is added in polyvinyl alcohol in silver nitrate in embodiment 1.
Fig. 2 is the XRD spectra that silver-colored chitosan/polyvinyl alcohol micro belt is carried obtained in embodiment 2.In figure a be chitosan/
The XRD curve of polyvinyl alcohol;B is the XRD curve for carrying silver-colored chitosan/polyvinyl alcohol.
Fig. 3 is the scanning electron microscopic picture that silver-colored chitosan/polyvinyl alcohol micro belt is carried obtained in embodiment 2.
Fig. 4 is that silver-colored chitosan/polyvinyl alcohol micro belt transmission electron microscope picture is carried obtained in embodiment 2.A is low power in figure
Transmit photo;B is that high power transmits photo.
Fig. 5 is the fungistatic effect figure that silver-colored chitosan/polyvinyl alcohol micro belt is carried obtained in embodiment 2.A is antibacterial in figure
Before;After b is antibacterial.
Specific embodiment
Below by specific embodiment and in conjunction with attached drawing, the invention will be further described, but not limited to this.
Chitosan used in embodiment is white or off-white powder, deacetylation > 95%, rank medical grade.It is used
Polyvinyl alcohol be white particle, model 1788, molecular weight 44.05MW.
Embodiment 1
It weighs 10g polyvinyl alcohol to be dissolved in 90g water, magnetic agitation dissolves by heating, and being made into 100g mass fraction is 10%
Poly-vinyl alcohol solution.It weighs 0.2g chitosan to be dissolved in lactic acid, is made into the chitosan lactic acid solution that 10g mass fraction is 2%.It will
After above-mentioned polyvinyl alcohol and chitosan solution are mixed with the mass ratio of 70:30, polyvinyl alcohol and chitosan gross mass 2% is added
Silver nitrate, be protected from light stirring 48h after be made into spinning solution.Spinning, voltage 20kV are carried out using electrostatic spinning apparatus, syringe pump pushes away
It is 2.26mL/h into speed, is received using aluminium foil, receiving distance is 15cm.Obtain the silver-colored chitosan/polyvinyl alcohol micro belt of load.
Obtained spinning solution is with the increase of mixing time, and UV absorption intensity is as shown in Figure 1, with mixing time
Increase, UV absorption intensity gradually increases, it was demonstrated that the reproducibility to silver ion of polyvinyl alcohol.
Embodiment 2
The mass concentration of poly-vinyl alcohol solution is expanded as 20%, other reagents and dosage and process conditions are constant, repeat
Embodiment 1 is to get to carrying silver-colored chitosan/polyvinyl alcohol micro belt.The XRD of obtained micro belt is as shown in Fig. 2, 20 ° or so
It is the unbodied peak of chitosan, the peak of indexing is the peak of elemental silver, illustrates that the silver in micro belt is elemental silver.Substrate carrier silver
The scanning of front and back and transmission photo difference are as shown in Figure 3,4, and obtained composite membrane is ribbon-like fibre, and diameter is 0.6-1 μm, carry
Ribbon-like fibre surface has uniformly been covered with silver nano-grain, partial size 5-60nm after silver.
Embodiment 3
The mass concentration of chitosan solution is expanded as 8%, other reagents and dosage and process conditions are constant, repeat to implement
Example 1 is to get to carrying silver-colored chitosan/polyvinyl alcohol micro belt.
Test example
The sample of embodiment 2 is tested into its bactericidal property using following methods:
Carry examination of the bactericidal property test of silver-colored chitosan/polyvinyl alcohol micro belt according to Appendix B in GB/T21510-2008
Proved recipe method, test strain are most representative Escherichia coli in gramnegative bacterium.Experiment uses shake-flask method, cut-parts
It is affixed on 250mL to be equipped in the conical flask of bacteria suspension, under the conditions of 25 DEG C, after 150r/min vibrates 2min, according to remaining in flask
Strain, test its bactericidal property.
Obtained bactericidal effect is survived after sterilization as shown in figure 5, have 504 E. coli clones in flask before sterilizing
Bacterium colony be 0, it is known that the sterilizing rate for carrying silver-colored chitosan/polyvinyl alcohol micro belt is 100%.