CN105854066B - Method of nanometer modified by silver polyelectrolyte membrane coating sericin gel and products thereof and application - Google Patents
Method of nanometer modified by silver polyelectrolyte membrane coating sericin gel and products thereof and application Download PDFInfo
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- CN105854066B CN105854066B CN201610232401.9A CN201610232401A CN105854066B CN 105854066 B CN105854066 B CN 105854066B CN 201610232401 A CN201610232401 A CN 201610232401A CN 105854066 B CN105854066 B CN 105854066B
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/32—Proteins, polypeptides; Degradation products or derivatives thereof, e.g. albumin, collagen, fibrin, gelatin
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/24—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/22—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons containing macromolecular materials
- A61L15/26—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L15/00—Chemical aspects of, or use of materials for, bandages, dressings or absorbent pads
- A61L15/16—Bandages, dressings or absorbent pads for physiological fluids such as urine or blood, e.g. sanitary towels, tampons
- A61L15/42—Use of materials characterised by their function or physical properties
- A61L15/44—Medicaments
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/10—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices containing or releasing inorganic materials
- A61L2300/102—Metals or metal compounds, e.g. salts such as bicarbonates, carbonates, oxides, zeolites, silicates
- A61L2300/104—Silver, e.g. silver sulfadiazine
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- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61L—METHODS OR APPARATUS FOR STERILISING MATERIALS OR OBJECTS IN GENERAL; DISINFECTION, STERILISATION OR DEODORISATION OF AIR; CHEMICAL ASPECTS OF BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES; MATERIALS FOR BANDAGES, DRESSINGS, ABSORBENT PADS OR SURGICAL ARTICLES
- A61L2300/00—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices
- A61L2300/40—Biologically active materials used in bandages, wound dressings, absorbent pads or medical devices characterised by a specific therapeutic activity or mode of action
- A61L2300/404—Biocides, antimicrobial agents, antiseptic agents
Abstract
The invention discloses method of nanometer modified by silver polyelectrolyte membrane coating sericin gel and products thereof and applications, wherein the method for nanometer modified by silver polyelectrolyte membrane coating sericin gel is first to prepare silk gum powder, silk gum porous gel is prepared again, then in silk gum porous gel pan coating polyelectrolyte membrane, finally in polyelectrolyte membrane coating sericin gel surface finish nano silver, nanometer modified by silver polyelectrolyte membrane coating sericin gel obtained has good biocompatibility, hygroscopicity, the anti-microbial property of moisture retention and high-efficient and lasting, it can be used for preparing anti-biotic material, it has a good application prospect.
Description
Technical field
The invention belongs to technical field of biological material, and in particular to the side of nanometer modified by silver polyelectrolyte membrane coating sericin gel
Method further relates to nanometer modified by silver polyelectrolyte membrane coating sericin gel and nanometer modified by silver polyelectrolyte obtained by this method
The application of film coating sericin gel.
Background technique
Fibroin mainly by fibroin albumen (fibroin) and is wrapped in the sericin (sericin) of its outer layer and constitutes,
Fibroin albumen is the main body of silk, accounts for about 75%；Remaining is sericin, accounts for about 25%.Sericin is wrapped around fibroin fibre
A kind of natural macromolecular viscous protein in dimension table face plays the role of protecting and being adhered to fibroin.Silk gum is by 18 kinds of amino acid groups
At wherein containing hydroxyl, carboxyl, amino etc. there is the amino acid of more highly polar side group to account for about the 70% of total amount.These amino acid
Impart the good bioactivity of silk gum and reactivity.Silk gum has wide in fields such as pharmacology, cosmetics, biomaterials
Wealthy application prospect.For a long time due to the deficiency that people recognize sericin, silk gum is caused to be taken as in filature industry
Waste processing.According to statistics, about 50000 tons of sericin or so lost every year with filature industry waste water stream in global range, are caused
Serious environmental pollution and the great wasting of resources.Under the Current resource overall situation in short supply with built environment friendly society,
The exploitation and recycling of silk gum function are particularly important.
As that studies silk gum gos deep into, scientific worker has found that sericin has moisturizing, antibacterial, antioxygen in recent years
Change, the biological nature of anticoagulation and promotion cellular adhesion and proliferation, and silk gum has good biocompatibility and biology
Degradability is ideal bio-medical material.Pure silk gum powder properties are fragile, are not easy to shape, in wet environment
It is easily corroded by bacterium, these problems greatly constrain the application range and the market competitiveness of silk gum product.Therefore research and development have
The silk gum anti-biotic material of good biocompatibility, certain mechanical property, shape and stability, gives full play to sericin
Advantage has important social and economic implications.
With the fast development of nanotechnology, the nano material of Various Functions to form product by developing, and is widely used in giving birth to
Every field living.Nano silver because of its excellent antibacterial and is killed using the anti-biotic material of new generation of modern nanotechnology preparation
Bacterium activity is widely used in biomedical such as wound repair field.Have some nanometers of silver products at present to apply to
Clinical medicine, such as nano silver gel, Nanometer silver dressing, nano silver conduit, nano silver bone cement.Nano silver grain has wide spectrum
Antibacterial activity, good inhibitory activity is all had for Gram-negative bacteria, gram-positive bacteria, fungi and virus.Yin Na
Rice corpuscles modification sericin gel material mainly passes through two ways: first is that the good silver nanoparticle deposition of pre-synthesis is coagulated in silk gum
The surface of glue material；Second is that the surface in situ in sericin gel material synthesizes Nano silver grain.The latter can be by Nano silver grain
Directly in sericin gel Surface Creation, step is simple, but since sericin gel surface can be used for adsorbing the chemical group of silver ion
It is limited, it is difficult to realize the payload of high density Nano silver grain, and the silver ion adsorbed is easy to fall off.Therefore, how to realize
Nano silver particles are the critical issues for urgently needing to solve in a large amount extended load on sericin gel surface.
Summary of the invention
In view of this, the present invention forms a strata electrolyte thin in porous sericin gel pan coating by chemical reaction
Film, then using it as three-dimensional rack fabricated in situ nano silver, so that the polyelectrolyte membrane for being prepared for nanometer modified by silver is coated
Sericin gel anti-biotic material, concrete scheme are as follows:
The method of nanometer modified by silver polyelectrolyte membrane coating sericin gel, 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) preparation of silk gum porous gel: silk gum powder obtained by step (1) is dissolved in water, and taking out after freezing keeps its heavy
Water suction, then freeze, it is finally freeze-dried, obtains silk gum porous gel；
(3) silk gum porous gel obtained by step (2) preparation of polyelectrolyte membrane coating sericin gel: is passed through into electrostatic layer
Layer self assembly obtains polyelectrolyte membrane coating sericin gel in sericin gel pan coating polyelectrolyte membrane；
(4) preparation of nanometer modified by silver polyelectrolyte membrane coating sericin gel: by polyelectrolyte membrane obtained by step (3)
It is coated with sericin gel in-situ reducing synthesizing nano-silver under the conditions of ultraviolet, it is solidifying to obtain nanometer modified by silver polyelectrolyte membrane coating silk gum
Glue.
In step (1) of the present invention, the preferred high temperature and high pressure method degumming of degumming, it is furthermore preferred that under the conditions of 120 DEG C, 0.1Mpa
20~30min of degumming, most preferably 20min.
In step (1) of the present invention, freeze can using arbitrarily can freezing temperature be refrigerated to complete icing, it is preferred that it is described
The condition freezed is -80 DEG C of freezing 2h.
In step (2) of the present invention, as long as silk gum powder is completely dissolved, silk gum powder concn is 8% (wt) effect
Most preferably, the water preferably by silk gum powder with temperature higher than 60 DEG C dissolves, more preferably using 80 DEG C or so temperature dissolutions；It can in freezing
Using arbitrarily can freezing temperature be refrigerated to complete icing, after being preferable over -20 DEG C of freezing 2h；Water suction is the sericin gel that will freeze again
Take out (18~25 DEG C) of room temperature placements；Freezing dry 12h preferably in freeze drier, obtains silk gum porous gel.
In step (3) of the present invention, a kind of effective Supramolecular self assembly method of electrostatic LBL self-assembly, by layer with
The intermolecular electrostatic of different charges, which interacts, between layer to form a strata electrolytic thin-membrane and is attached to the surface of material, to assign
Give the different performance of material.This self-assembled film has the advantages that a variety of: experimental method is simple, is easy to repeat；Between layers
It is combined together by strong electrostatic interactions, improves the stability of membrane structure；It is applied widely.Theoretically,
Any molecule with opposite charges can be self-assembly of polyelectrolyte membrane by this method.This method has stronger
Practicability can not only increase the specific surface of sericin gel in the one strata electrolytic thin-membrane of pan coating of silk gum porous gel
Product improves the load capacity of silver nanoparticle ion, and can enhance silver nanoparticle ion by electrostatic adsorption and polyelectrolyte is thin
The combination of film, to assign sericin gel long-acting enduringly antibacterial activity.The polyelectrolyte membrane of sericin gel pan coating can
2 layers or 2 layers or more are thought, wherein the double-deck polyelectrolyte membrane coating sericin gel is preferably poly propenoic acid acrylic acid
Layer and dimethyl diallyl ammonium chloride/polypropylene acid layer, preparation method are as follows: by silk gum porous gel first in poly- ethyleneimine
It impregnates in solution, then is impregnated in polyacrylic acid solution, then impregnate in dimethyl diallyl ammonium chloride solution, then exist
It is impregnated in polyacrylic acid solution, obtains polyelectrolyte membrane coating sericin gel.Preferably, the concentration of the poly- ethyleneimine solution is
1% (w/v, g/ml)；The concentration of the polyacrylic acid solution is 1% (w/v, g/ml)；The dimethyl diallyl ammonium chloride
The concentration of solution is 1% (w/v, g/ml)；The time of the immersion is 1~5min.
In the present invention, step (4) is to do the coating sericin gel of polyelectrolyte membrane obtained by step (3) at 18-25 DEG C
It is dry, it is then placed in the AgNO that concentration is 10~50mM3In, it is taken out after closed irradiation at least 10min under 365nm ultraviolet light, 18-
25 DEG C are dried to obtain a nanometer modified by silver polyelectrolyte membrane coating sericin gel.Preferably, the closed irradiation under 365nm ultraviolet light
10~60min.
The second object of the present invention is to provide nanometer modified by silver polyelectrolyte membrane coating silk prepared by the above method
Glue gel, the sericin gel have the anti-microbial property of good biocompatibility, hygroscopicity, moisture retention and high-efficient and lasting, specifically
Scheme is as follows:
The nanometer modified by silver polyelectrolyte membrane as made from the method is coated with sericin gel.
The third object of the present invention is to provide a nanometer application for modified by silver polyelectrolyte membrane coating sericin gel, specifically
Side is by as follows:
The nanometer modified by silver polyelectrolyte membrane coating sericin gel is preparing the application in anti-biotic material.
Preferably, the anti-biotic material is resisting gram-positive bacteria material or/and Gram-negative bacteria material, the anti-leather
Lan Shi positive bacteria is Escherichia coli, and the Gram-negative bacteria is staphylococcus aureus.
The beneficial effects of the present invention are: the present invention utilizes freeze-drying by successfully extracting sericin from silk cocoon
Method is successfully prepared the sericin gel with loose and porous structure, then by electrostatic interaction on sericin gel surface
It is coated with polyelectrolyte membrane, using the method for Electrostatic Absorption, in-situ reducing synthesizing nano-silver under the conditions of ultraviolet is prepared for nanometer
Modified by silver polyelectrolyte membrane is coated with silk gum porous gel, and this method is easy to operate, mild condition, and nanometer modified by silver obtained is poly-
Electrolytic thin-membrane, which is coated with silk gum porous gel, has good biocompatibility, hygroscopicity, the antibacterial of moisture retention and high-efficient and lasting
Performance can be used for the related biomaterial for medical purpose such as antiseptic dressing field, overcome sericin material and be easy to breed bacterium not
Foot, has 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:
Fig. 1 is the preparation principle schematic diagram that nanometer modified by silver polyelectrolyte membrane is coated with sericin gel.
Fig. 2 is that nanometer modified by silver polyelectrolyte membrane is coated with sericin gel surface Scanning Electron in sericin gel preparation process
(A: polyelectrolyte membrane is coated with sericin gel to microscope figure；B: sericin gel is placed at 50mM AgNO3Ultraviolet irradiation in solution
10min；C: polyelectrolyte membrane modification sericin gel is placed at 50mM AgNO3Ultraviolet irradiation 10min in solution；D: poly- electrolysis
Matter film coating sericin gel is placed at 50mM AgNO3Ultraviolet irradiation 30min in solution).
Fig. 3 is that nanometer modified by silver polyelectrolyte membrane is coated with sericin gel XRD spectrum (A: silk gum porous gel；B: poly- electricity
It solves matter film and is coated with sericin gel；C: nanometer modified by silver polyelectrolyte membrane is coated with sericin gel).
Fig. 4 is that nanometer modified by silver polyelectrolyte membrane is coated with sericin gel DSC map (A: silk gum porous gel；B: poly- electricity
It solves matter film and is coated with sericin gel；C: nanometer modified by silver polyelectrolyte membrane is coated with sericin gel).
Fig. 5 is that addition nanometer modified by silver polyelectrolyte membrane is coated with Escherichia coli and staphylococcus aureus after sericin gel
Growth curve (A: the growth curve of Escherichia coli；B: the growth curve of staphylococcus aureus；A: blank control；B: silk gum
Gel；C: polyelectrolyte membrane is coated with sericin gel；D: nanometer modified by silver polyelectrolyte membrane is coated with sericin gel).
Fig. 6 is that addition nanometer modified by silver polyelectrolyte membrane is coated with Escherichia coli and staphylococcus aureus after sericin gel
Inhibition zone (A: the antibacterial loop graph of Escherichia coli；B: the antibacterial loop graph of staphylococcus aureus；A: sericin gel；B: poly- electrolysis
Matter film is coated with sericin gel；C: nanometer modified by silver polyelectrolyte membrane is coated with sericin gel).
Specific embodiment
Below in conjunction with attached drawing, a preferred embodiment of the present invention will be described in detail.It is not specified in embodiment specific
The experimental method of condition, usually according to conventional conditions or according to the manufacturer's recommendations.
Nanometer modified by silver polyelectrolyte membrane is coated with sericin gel, and schematic diagram is as shown in Figure 1, particular by high temperature height
The method of pressure is successfully extracted sericin from silkworm silk cocoon, using the method for freeze-drying, is successfully prepared with loose porous
Then the sericin gel of structure is inhaled in sericin gel pan coating polyelectrolyte membrane using electrostatic by electrostatic interaction
It is solidifying to be prepared for nanometer modified by silver polyelectrolyte membrane coating silk gum for attached method in-situ reducing synthesizing nano-silver under the conditions of ultraviolet
Glue.The gel has the anti-microbial property of good biocompatibility, hygroscopicity, moisture retention and high-efficient and lasting, can be used for antibacterial and applies
The related biomaterial for medical purpose such as material field.
Embodiment 1
The method of nanometer modified by silver polyelectrolyte membrane coating sericin gel, includes the following steps:
(1) preparation of silk gum powder: taking 10g silk cocoon to be cut into fractionlet, is that 1:30 is placed in high-pressure sterilizing pot by bath raio
(120 DEG C, 0.1Mpa) high pressure 20min, the silk after high pressure is wrung out, and obtains silk gum solution, -80 DEG C of freezings with filtered through gauze
2h is placed in freeze drier for 24 hours, obtains silk gum powder；
(2) preparation of silk gum porous gel: by silk gum powder hot water (80 DEG C) weight obtained by step (1) it is molten be 8% (wt)
Solution pours into mold, and 2h is then freezed in -20 DEG C of refrigerator, and taking-up allows after its heavy water suction, is placed again into -20 DEG C of refrigerators
2h is freezed, 12h in freeze drier is subsequently placed in, obtains silk gum porous gel；
(3) preparation of polyelectrolyte membrane coating sericin gel: sericin gel obtained by step (2) is sliced, in 1% (w/
V) impregnate 1min in poly- ethyleneimine (PEI) solution, then impregnate 1min in the polyacrylic acid (PAA) of 1% (w/v), obtain with
Sericin gel is that the polyelectrolyte membrane of substrate is coated with sericin gel；
(4) preparation of the double-deck polyelectrolyte membrane coating sericin gel: base's polyelectrolyte membrane obtained by step (3) is repaired
The sericin gel of decorations impregnates 1min in dimethyl diallyl ammonium chloride (PDDA) solution that concentration is 1% (w/v), then dense
1min is impregnated in polyacrylic acid (PAA) solution that degree is 1% (w/v), the double-deck polyelectrolyte membrane is obtained and is coated with sericin gel,
Middle bilayer polyelectrolyte membrane is respectively PEI/PAA layers and PDDA/PAA layers；
(5) preparation of nanometer modified by silver polyelectrolyte membrane coating sericin gel: by the double-deck polyelectrolyte obtained by step (4)
Film is coated with sericin gel drying under room temperature (18-25 DEG C), is then placed in the AgNO that concentration is 50mM3In, it is ultraviolet in 365nm
It is taken out after closed irradiation 30min under light, it is solidifying that room temperature (18-25 DEG C) is dried to obtain nanometer modified by silver polyelectrolyte membrane coating silk gum
Glue.
Embodiment 2
The method of nanometer modified by silver polyelectrolyte membrane coating sericin gel, includes the following steps:
(1) preparation of silk gum powder: taking 10g silk cocoon to be cut into fractionlet, is that 1:30 is placed in high-pressure sterilizing pot by bath raio
(120 DEG C of 0.1Mpa) high pressure 20min, the silk after high pressure is wrung out, obtains silk gum solution with filtered through gauze；- 80 DEG C of freezing 2h,
It is placed in freeze drier for 24 hours, obtains silk gum powder；
(2) preparation of silk gum porous gel: by silk gum powder hot water (80 DEG C) weight obtained by step (1) it is molten be 8% (wt)
Solution pours into mold, and 2h is then freezed in -20 DEG C of refrigerator, and taking-up allows after its heavy water suction, is placed again into -20 DEG C of refrigerators
2h is freezed, 12h in freeze drier is subsequently placed in, obtains silk gum porous gel；
(3) preparation of polyelectrolyte membrane coating sericin gel: sericin gel obtained by step (2) is sliced, in 1% (w/
V) impregnate 3min in poly- ethyleneimine (PEI) solution, then impregnate 3min in the polyacrylic acid (PAA) of 1% (w/v), obtain with
Sericin gel is that the polyelectrolyte membrane of substrate is coated with sericin gel；
(4) preparation of the double-deck polyelectrolyte membrane coating sericin gel: base's polyelectrolyte membrane obtained by step (3) is repaired
The sericin gel of decorations impregnates 3min in dimethyl diallyl ammonium chloride (PDDA) solution that concentration is 1% (w/v), then dense
3min is impregnated in polyacrylic acid (PAA) solution that degree is 1% (w/v), the double-deck polyelectrolyte membrane is obtained and is coated with sericin gel,
Middle bilayer polyelectrolyte membrane is respectively PEI/PAA layers and PDDA/PAA layers；
(5) preparation of nanometer modified by silver polyelectrolyte membrane coating sericin gel: by the double-deck polyelectrolyte obtained by step (4)
Film is coated with sericin gel drying under room temperature (18-25 DEG C), is then placed in the AgNO that concentration is 50mM3In, it is ultraviolet in 365nm
It is taken out after closed irradiation 30min under light, it is solidifying that room temperature (18-25 DEG C) is dried to obtain nanometer modified by silver polyelectrolyte membrane coating silk gum
Glue.
Embodiment 3
The method of nanometer modified by silver polyelectrolyte membrane coating sericin gel, includes the following steps:
(1) preparation of silk gum powder: taking 10g silk cocoon to be cut into fractionlet, is placed in high-pressure sterilizing pot by bath raio 1:30
(120 DEG C of 0.1Mpa) high pressure 20min, the silk after high pressure is wrung out, and obtains silk gum solution with filtered through gauze, -80 DEG C of freezing 2h,
It is placed in freeze drier for 24 hours, obtains silk gum powder；
(2) preparation of silk gum porous gel: by silk gum powder hot water (80 DEG C) weight obtained by step (1) it is molten be 8% (wt)
Solution pours into mold, and 2h is then freezed in -20 DEG C of refrigerator, and taking-up allows after its heavy water suction, is placed again into -20 DEG C of refrigerators
2h is freezed, 12h in freeze drier is subsequently placed in, obtains silk gum porous gel；
(3) preparation of polyelectrolyte membrane coating sericin gel: sericin gel obtained by step (2) is sliced, in 1% (w/
V) impregnate 5min in poly- ethyleneimine (PEI) solution, then impregnate 5min in the polyacrylic acid (PAA) of 1% (w/v), obtain with
Sericin gel is that the polyelectrolyte membrane of substrate is coated with sericin gel；
(4) preparation of the double-deck polyelectrolyte membrane coating sericin gel: base's polyelectrolyte membrane obtained by step (3) is repaired
The sericin gel of decorations impregnates 5min in dimethyl diallyl ammonium chloride (PDDA) solution that concentration is 1% (w/v), then dense
5min is impregnated in polyacrylic acid (PAA) solution that degree is 1% (w/v), the double-deck polyelectrolyte membrane is obtained and is coated with sericin gel,
Middle bilayer polyelectrolyte membrane is respectively PEI/PAA layers and PDDA/PAA layers；
(5) preparation of nanometer modified by silver polyelectrolyte membrane coating sericin gel: by the double-deck polyelectrolyte obtained by step (4)
Film is coated with sericin gel drying under room temperature (18-25 DEG C), is then placed in the AgNO that concentration is 50mM3In, it is ultraviolet in 365nm
It is taken out after closed irradiation 30min under light, it is solidifying that room temperature (18-25 DEG C) is dried to obtain nanometer modified by silver polyelectrolyte membrane coating silk gum
Glue.
Nanometer modified by silver polyelectrolyte membrane made from Examples 1 to 3 is coated with sericin gel electron microscope scanning,
As a result as shown in Figure 2.The results show that silk gum porous gel is capable of forming supporting structure after polyelectrolyte membrane is modified, will gather
Electrolytic thin-membrane is coated with sericin gel in 50mM AgNO3Can be in surface finish nano silver after ultraviolet irradiation in solution, and receive
The sericin gel that rice modified by silver amount increases as irradiation time increases, and is not coated with polyelectrolyte membrane is only capable of modification and receives on a small quantity
Meter Yin shows to show that being coated with polyelectrolyte membrane can be improved the load capacity of silver nanoparticle ion in sericin gel.
Then by the coating sericin gel of nanometer modified by silver polyelectrolyte membrane made from Examples 1 to 3 with carrying out XRD spectrum
Analysis, as a result as shown in Figure 3.The result shows that nano silver, which is successfully modified, is coated with sericin gel surface in polyelectrolyte membrane.
The coating sericin gel of nanometer modified by silver polyelectrolyte membrane made from Examples 1 to 3 is divided with DSC map is carried out
Analysis, as a result as shown in Figure 4.The result shows that the success of sericin gel surface is coated with by polyelectrolyte membrane, and polyelectrolyte membrane packet
Shown also to succeed by nanometer modified by silver by sericin gel, illustrates that a nanometer modified by silver polyelectrolyte membrane coating sericin gel is successfully made
?.
The bacteriostatic experiment of embodiment 4, nanometer modified by silver polyelectrolyte membrane coating sericin gel
1, growth curve is tested
The present embodiment is by being added sericin gel, polyelectrolyte membrane coating sericin gel to the bacterium grown naturally or receiving
The growth curve of bacteria of rice modified by silver polyelectrolyte membrane coating sericin gel compares, so that it is determined that the silk of nanometer modified by silver
The antibacterial effect of glue gel, method particularly includes:
(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, cultivate 12h under the conditions of revolving speed is 220rpm, temperature is 37 DEG C；
(2) Escherichia coli and 100 μ L of staphylococcus aureus bacteria suspension for taking step (1) to activate respectively are added to 10mL
In LB culture medium, every kind of bacterium solution prepares 4 groups, wherein one group is blank group, remaining 3 groups are separately added into sericin gel, polyelectrolyte
Film is coated with sericin gel and nanometer modified by silver polyelectrolyte membrane is coated with sericin gel, is then 220rpm, temperature in revolving speed
Cultivated under the conditions of being 37 DEG C, and 0h, 1h, 2h, 3h, 4h, 6h, 8h, 12h, 18h, for 24 hours, 30h and 36h when take bacteria suspension
0.5mL, in 4 DEG C of Storage in refrigerator；
(3) bacteria suspension that different time takes out is taken out from 4 DEG C of refrigerators after the bacteria suspension wait cultivate 36h samples, 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.It is solidifying to analyze silk gum
The shadow of glue, polyelectrolyte membrane coating sericin gel and nanometer modified by silver polyelectrolyte membrane coating sericin gel to bacterial growth
It rings, the results show that after addition nanometer modified by silver polyelectrolyte membrane coating sericin gel, Escherichia coli and staphylococcus aureus
Growth receive obvious inhibition, show that nanometer modified by silver polyelectrolyte membrane prepared by the present invention coating sericin gel has
Excellent anti-microbial property.
2, Bactericidal test
To further determine that nanometer modified by silver polyelectrolyte membrane is coated with the antibacterial action of sericin gel, inhibition zone is utilized
Method tests the coated sericin gel of polyelectrolyte membrane of nanometer modified by silver to Escherichia coli and staphylococcus aureus
Fungistatic effect, the specific method is as follows:
(1) single colonie of Escherichia coli and staphylococcus aureus is taken to be inoculated in the 100mL LB Liquid Culture of sterilizing respectively
In base (pH 7.4), 10h is cultivated 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 being diluted 100 times,
And 1-2h is cultivated in the shaking table that revolving speed is 220rpm, so that dilution is evenly distributed on agar media surface；
(3) taking diameter is the sericin gel of 1cm, polyelectrolyte membrane coating sericin gel and nanometer modified by silver polyelectrolyte
Film is coated with sericin gel, is laid in the LB media surface that dilution is evenly distributed；Then 12h is cultivated under the conditions of 37 DEG C,
As a result as shown in Figure 6.The results show that being inoculated with the culture medium of Escherichia coli in the LB culture medium for being placed with sericin gel and connecing
Apparent inhibition zone is not formed on the culture medium of kind staphylococcus aureus, shows life of the sericin gel to Escherichia coli itself
Long no inhibiting effect, and in the LB culture medium for placing polyelectrolyte membrane coating sericin gel, it all observes and forms one
Fixed inhibition zone shows that polyelectrolyte membrane itself has a certain impact to the growth of bacterium.And it is being placed with a nanometer modified by silver
Polyelectrolyte membrane is coated in the culture medium of sericin gel, it can be observed that foring apparent inhibition zone, shows that nano silver is repaired
The coated sericin gel of the polyelectrolyte membrane of decorations has significant bacteriostasis.
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 (9)
1. the method for nanometer modified by silver polyelectrolyte membrane coating sericin gel, which comprises the steps of:
(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；The degumming is 20 ~ 30min of degumming under the conditions of 120 DEG C, 0.1 Mpa；
(2) preparation of silk gum porous gel: silk gum powder obtained by step (1) is dissolved in water, and taking out after freezing makes its heavy water suction,
Freeze again, be finally freeze-dried, obtains silk gum porous gel；
(3) silk gum porous gel obtained by step (2) preparation of polyelectrolyte membrane coating sericin gel: is passed through into electrostatic layer by layer certainly
It is assembled in sericin gel pan coating polyelectrolyte membrane, obtains polyelectrolyte membrane coating sericin gel；
(4) preparation of nanometer modified by silver polyelectrolyte membrane coating sericin gel: polyelectrolyte membrane obtained by step (3) is coated with
Sericin gel in-situ reducing synthesizing nano-silver under the conditions of ultraviolet obtains a nanometer modified by silver polyelectrolyte membrane coating sericin gel.
2. the method for nanometer modified by silver polyelectrolyte membrane coating sericin gel according to claim 1, it is characterised in that: step
Suddenly in (1), the condition freezed is -80 DEG C of 2 h of freezing.
3. the method for nanometer modified by silver polyelectrolyte membrane coating sericin gel according to claim 1, it is characterised in that: institute
Stating step (2) is that the water by silk gum powder temperature higher than 60 DEG C dissolves, and taking-up allows its heavy water suction after -20 DEG C of 2 h of freezing,
Again in -20 DEG C of 2 h of freezing, 12 h are finally freeze-dried, silk gum porous gel is obtained.
4. the method for nanometer modified by silver polyelectrolyte membrane coating sericin gel according to claim 1, it is characterised in that: institute
Stating step (3) is first to impregnate silk gum porous gel obtained by step (2) in poly- ethyleneimine solution, then in polyacrylic acid solution
It impregnates, then impregnates in dimethyl diallyl ammonium chloride solution, then impregnated in polyacrylic acid solution, obtain polyelectrolyte
Film is coated with sericin gel.
5. the method for nanometer modified by silver polyelectrolyte membrane coating sericin gel according to claim 4, it is characterised in that: institute
The concentration for stating poly- ethyleneimine solution is 1%(w/v, g/ml)；The concentration of the polyacrylic acid solution is 1%(w/v, g/ml)；It is described
The concentration of dimethyl diallyl ammonium chloride solution is 1%(w/v, g/ml)；The time of the immersion is 1 ~ 5 min.
6. the method for any one nanometer modified by silver polyelectrolyte membrane coating sericin gel according to claim 1 ~ 5, special
Sign is: step (4) is to be then placed in the drying at 18-25 DEG C of the coating sericin gel of polyelectrolyte membrane obtained by step (3)
Concentration is the AgNO of 10 ~ 50 mM3In, it is taken out after closed irradiation at least 10 min under 365 nm ultraviolet lights, 18-25 DEG C of drying
Obtain a nanometer modified by silver polyelectrolyte membrane coating sericin gel.
7. the nanometer modified by silver polyelectrolyte membrane as made from any one of claim 1 ~ 6 the method is coated with sericin gel.
8. the coating sericin gel of nanometer modified by silver polyelectrolyte membrane described in claim 7 is preparing the application in anti-biotic material.
9. application according to claim 8, it is characterised in that: the anti-biotic material be resisting gram-positive bacteria material or/
With Gram-negative bacteria material.
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| CN106633161A (en) * | 2016-11-30 | 2017-05-10 | 西南大学 | Preparation method of sericin-polyvinyl alcohol blended antibacterial film loaded with nano-silver, and product and application of antibacterial film |
| CN106751920B (en) * | 2016-12-01 | 2019-07-09 | 西南大学 | Preparation method of the enhanced laminated film anti-biotic material of polyvinyl alcohol-silk gum-nano silver and products thereof and application |
| CN108250478A (en) * | 2018-01-30 | 2018-07-06 | 西南大学 | Preparation method of the coated silk gum of nanometer modified by silver polyelectrolyte layer/agar composite membrane and products thereof and application |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182348A (en) * | 2007-10-19 | 2008-05-21 | 浙江大学 | Preparation method of frozen sericin gel |
| CN103665894A (en) * | 2013-11-11 | 2014-03-26 | 青岛佰众化工技术有限公司 | Nanometer silk fibroin-nano-silver antibacterial composite material |
| CN103882718A (en) * | 2014-04-11 | 2014-06-25 | 西南大学 | Preparation method of silk modified by nano-silver as well as product and application of silk modified by nano-silver |
| CN204501804U (en) * | 2014-04-23 | 2015-07-29 | 金陵科技学院 | A kind of medical nano-silver combine dressing |
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| ITVR20010098A1 (en) * | 2001-09-11 | 2003-03-11 | Consorzio Per Gli Studi Uni | PROCEDURE FOR OBTAINING SILK FIBROIN HYDROGELS. |
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- 2016-04-14 CN CN201610232401.9A patent/CN105854066B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101182348A (en) * | 2007-10-19 | 2008-05-21 | 浙江大学 | Preparation method of frozen sericin gel |
| CN103665894A (en) * | 2013-11-11 | 2014-03-26 | 青岛佰众化工技术有限公司 | Nanometer silk fibroin-nano-silver antibacterial composite material |
| CN103882718A (en) * | 2014-04-11 | 2014-06-25 | 西南大学 | Preparation method of silk modified by nano-silver as well as product and application of silk modified by nano-silver |
| CN204501804U (en) * | 2014-04-23 | 2015-07-29 | 金陵科技学院 | A kind of medical nano-silver combine dressing |
Non-Patent Citations (2)
| Title |
|---|
| Preparation and characterization of a novel spony hydrogel from aqueous Bombyx mori sericin;Haiping Zhang等;《e-polymers》;20080526(第066期);第8-9页"Experimental part"部分 |
| Preparation and characterization of sericin powder extracted from silk industry wastewater;Jin-Hong Wu等;《Food Chemistry》;20061228;第103卷(第4期);1255-1262 |
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