CN114032691A - Flat-plate silk antibacterial composite material and preparation method thereof - Google Patents
Flat-plate silk antibacterial composite material and preparation method thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 48
- 108010039918 Polylysine Proteins 0.000 claims abstract description 38
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- LMDZBCPBFSXMTL-UHFFFAOYSA-N 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide Chemical compound CCN=C=NCCCN(C)C LMDZBCPBFSXMTL-UHFFFAOYSA-N 0.000 description 32
- 241000255789 Bombyx mori Species 0.000 description 29
- 238000009987 spinning Methods 0.000 description 18
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- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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- D—TEXTILES; PAPER
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- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
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Abstract
The invention discloses a flat filament antibacterial composite material and a preparation method thereof. The antibacterial material comprises flat filaments and epsilon-polylysine crosslinked on the surfaces of the flat filaments, and has good antibacterial ability, biocompatibility and degradability; meanwhile, the preparation method of the antibacterial material is also very simple, and mainly comprises the following steps: putting the flat plate silk into a ternary solution for surface treatment, and taking out the flat plate silk for later use when the surface of the flat plate silk is slightly dissolved but the complete structure state is kept; and grafting epsilon-polylysine on the surface of the flat silk after surface treatment by using a cross-linking agent to obtain the antibacterial material.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials, and particularly relates to a flat-plate silk antibacterial composite material and a preparation method thereof.
Background
With the rapid development of society and the improvement of living standard of people, more and more people find that harmful microorganisms such as bacteria, mold and the like seriously harm the health, the living quality and the living environment of human beings. Currently, over 70% of bacterial infections require the use of one or more antibiotics to be completely eradicated, but the use of antibiotics can result in resistance, and the use of antibacterial materials is therefore of increasing concern. The antibacterial material is a functional material capable of killing harmful bacteria and inhibiting growth and reproduction of the harmful bacteria, and the effective component of the antibacterial material is an antibacterial agent. The antibacterial material can effectively prevent bacteria from breeding and reduce the harm of bacteria to human bodies from the source. Particularly, biomedical materials are required to have a certain antibacterial property, so that series of complications caused by bacterial infection in the process of treating diseases are reduced.
The effective biomedical antibacterial material not only requires excellent antibacterial property of the material, but also has the functions of proper structure, proper degradation rate, good biocompatibility, moisture absorption and breathability and the like so as to accelerate the treatment of diseases and the rehabilitation of patients. The epsilon-polylysine (epsilon-poly-L-lysine, epsilon-PL) is a polymer formed by connecting alpha-amino and epsilon-carboxyl of L-lysine through amido bond, is generated in the fermentation process of streptomyces albus, and is a biological metabolic product with good antibacterial performance. In an acidic or weakly acidic environment, epsilon-polylysine has a certain bacteriostatic effect on saccharomycetes, mould, gram-positive bacteria and gram-negative bacteria, has good water solubility and thermal stability, does not have teratogenicity and mutability, is easy to biodegrade, and can be widely applied to the fields of food, medicine and the like. Silk is a precious natural organic polymer material, and is one of the earliest utilized natural proteins for human beings. The silk is mainly composed of sericin and silk fibroin and is rich in 18 amino acids. Because of its advantages of good biocompatibility, degradability, air and moisture permeability, and low inflammatory reaction, silk is widely concerned by researchers in the biomedical and material science fields of various countries in the world.
The flat silk is a silk material with a silkworm cocoon structure obtained by spinning mature silkworms on a two-dimensional plane, and the delicate cocoon layer structure provides effective protection for the silkworm body in the sensitive period of pupation due to metamorphosis and development into moths, which is consistent with the protection of human skin from the change and stimulation of the external environment. The size of the flat wire is controllable, and the repairability is strong, so that the flat wire antibacterial material with different sizes or functions can be designed according to requirements.
Disclosure of Invention
The invention aims to: the flat-plate wire antibacterial composite material and the preparation method thereof are provided, the prepared antibacterial material is good in antibacterial performance, excellent in biocompatibility and degradable, the preparation steps are simple, and large-scale production is facilitated.
The technical scheme adopted by the invention is as follows:
the antibacterial composite material comprises flat wires and epsilon-polylysine cross-linked on the surfaces of the flat wires.
The preparation method of the flat wire antibacterial composite material comprises the following steps:
(1) putting the flat plate silk into a ternary solution for surface treatment, and taking out the flat plate silk for later use when the surface of the flat plate silk is slightly dissolved but the complete structure state is kept;
(2) and grafting epsilon-polylysine on the surface of the flat silk subjected to surface treatment by using a cross-linking agent to obtain the antibacterial material.
Further, before surface treatment of the flat wire, hot pressing is carried out on the flat wire, wherein the hot pressing time is 1-10min, the hot pressing temperature is 60-180 ℃, and the hot pressing pressure is 5-15 MPa.
Further, the ternary solution is prepared from anhydrous calcium chloride, anhydrous ethanol and water, wherein the weight ratio of the anhydrous calcium chloride: anhydrous ethanol: the molar ratio of water is 1:2: 8.
Further, during the surface treatment, the soaking time in the ternary solution is 3-30min, and the soaking temperature is 40-60 ℃.
Further, the cross-linking agent comprises EDC and NHS, and the mass ratio of EDC to NHS is 1: 1.
Furthermore, during cross-linking, the flat-plate silk subjected to surface treatment is immersed into MES solution, and then the cross-linking agent and the epsilon-polylysine are added, so that the epsilon-polylysine is cross-linked on the surface of the flat-plate silk.
Furthermore, the concentration of the MES solution is 0.1mol/ml, the mass ratio of the MES solution to the flat filament is 1:10, the addition amount of EDC and NHS is 2-10mg/ml, and the addition amount of epsilon-polylysine is 10-100 mg/ml.
Furthermore, the reaction temperature during crosslinking is 18-60 ℃, and the reaction time is 1-24 h.
Further, the thickness of the flat wire is 0.5-5 mm.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. the antibacterial material has good biocompatibility, is beneficial to cell adhesion and proliferation, has certain degradability, can be used as an antibacterial dressing or a tissue engineering material, and has good application prospect;
2. the antibacterial material has good inhibition effect on saccharomycetes, mould, gram-positive bacteria and gram-negative bacteria, and has good water solubility and thermal stability;
3. the flat wire is used as a substrate material, the size of the flat wire is controllable, the modifiability is strong, the size can be designed according to the use requirement during production, and the use is very convenient;
4. the preparation steps of the antibacterial material are simple, and only epsilon-polylysine needs to be grafted on the surface of the flat plate yarn, so that the large-scale production is facilitated;
5. before surface treatment, the flat wire is hot-pressed, so that the flat wire is relatively compact in structure, and the performance of the prepared antibacterial material can be effectively improved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
FIG. 1 shows the experimental results of the zone of inhibition of bacteria of the material;
fig. 2 shows SEM scanning observation results.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the detailed description and specific examples, while indicating the preferred embodiment of the invention, are intended for purposes of illustration only and are not intended to limit the scope of the invention. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
It is to be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The invention provides a flat-plate silk antibacterial composite material which comprises flat-plate silk and epsilon-polylysine crosslinked on the surface of the flat-plate silk.
The material has good biocompatibility, excellent antibacterial performance and certain degradability, and is very suitable for being used in the field of biomedical materials such as tissue engineering skin, antibacterial dressings and the like.
The preparation method of the material comprises the following steps:
putting the flat plate silk into a ternary solution for surface treatment, and taking out the flat plate silk for later use when the surface of the flat plate silk is slightly dissolved but the complete structure state is kept;
and grafting epsilon-polylysine on the surface of the flat silk subjected to surface treatment by using a cross-linking agent to obtain the antibacterial material.
The flat silk is prepared by putting five-instar mature silkworms on a two-dimensional plane silk spinning plate for spinning, the mature silkworms can be tussah silkworms or silkworm silkworms, and the flat silk obtained by the method consists of sericin and silk fibroin, has a porous hierarchical non-woven structure similar to silkworm cocoons, is a natural biomass composite material, has excellent physical and chemical properties, and is degradable. Certainly, in order to obtain better flat silk, silkworms can be fed under the conditions of 25 ℃ and 75% -80% of humidity, fresh mulberry leaves are used for feeding, and the illumination period is (light/dark): 12h/12 h. Wherein, the thickness of the flat wire is generally controlled to be 0.5-5mm, so that the use is not influenced while better performance is obtained.
Meanwhile, before the surface treatment of the flat wire, the flat wire is preferably subjected to hot pressing treatment to ensure that the flat wire has a compact structure, wherein the hot pressing treatment time is 1-10min, the hot pressing temperature is 60-180 ℃, and the hot pressing pressure is 5-15 MPa.
Wherein, the ternary solution is prepared by anhydrous calcium chloride, absolute ethyl alcohol and water, and the weight ratio of the anhydrous calcium chloride: anhydrous ethanol: the molar ratio of water is 1:2:8, and in the surface treatment, the immersion time of the plate silk in the ternary solution is 3-30min, the immersion temperature is 40-60 ℃, so that the surface of the plate silk is slightly dissolved, but the complete structure state is not influenced, and the grafting effect of epsilon-polylysine is better.
The cross-linking agent is preferably a mixture of EDC (1-ethyl-3- (3-dimethylaminopropyl) -carbodiimide) and NHS (N-hydroxysuccinimide), wherein the mass ratio of EDC to NHS is 1:1, so that the EDC and the NHS can better perform an activation reaction with flat filaments, and epsilon-polylysine is grafted, and the prepared material has good antibacterial capability.
Specifically, during crosslinking, firstly, the flat wire subjected to surface treatment is immersed in MES solution, and then a crosslinking agent and epsilon-polylysine are added to crosslink the epsilon-polylysine on the surface of the flat wire, wherein the concentration of the MES solution is 0.1mol/ml, the bath ratio is 1:10, the addition amounts of EDC and NHS are both 2-10mg/ml, and the addition amount of the epsilon-polylysine is 10-100 mg/ml. The reaction temperature of the crosslinking can be room temperature to 60 ℃, particularly 18-60 ℃, and the reaction time is 1-24 h.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
A preparation method of a flat wire antibacterial composite material comprises the following steps:
(1) normally feeding the silkworm strain 932-five years old under the conditions of room temperature of 25 ℃ and humidity of 75% -80%, feeding fresh mulberry leaves, and ensuring the illumination period (light/dark): adding fresh folium Mori every 8 hr for 12 hr/12 hr;
(2) placing a plurality of mature silkworms with defecation and urination clustered on a two-dimensional plane for spinning, wherein the density of the mature silkworms on a spinning plate is 500 heads/m2Checking every 3 hours in the spinning process, and adjusting the density and uniformity of silkworms to obtain flat silks with the thickness of 1 mm;
(3) and putting the flat silk into a hot pressing plate for hot pressing. The hot-pressing preheating time is 30s, the hot-pressing time is 1min, the hot-pressing temperature is 80 ℃, and the hot-pressing strength is 10 MPa;
(4) putting the flat wire into a ternary solution for pretreatment, wherein the treatment temperature is 50 ℃, and the treatment time is 10 min;
(5) cleaning the pretreated flat wire with deionized water for 3 times, and cleaning with MES for 1 time for later use;
(6) putting the cleaned flat silk into MES solution at a bath ratio of 1:10, adding EDC and NHS, wherein the addition amount of EDC and NHS is 5mg/mL, and then adding epsilon-polylysine, wherein the addition amount of epsilon-polylysine is 20mg/mL, 60mg/mL, 100mg/mL and 140mg/mL respectively, and carrying out shake reaction for 3h at a constant temperature of 40 ℃ to obtain 4 antibacterial materials with different epsilon-polylysine contents.
Example 2
A preparation method of a flat wire antibacterial composite material comprises the following steps:
(1) normally feeding the silkworm strain 932-five years old under the conditions of room temperature of 25 ℃ and humidity of 75% -80%, feeding fresh mulberry leaves, and ensuring the illumination period (light/dark): adding fresh folium Mori every 8 hr for 12 hr/12 hr;
(2) placing a plurality of mature silkworms with defecation and urination clustered on a two-dimensional plane for spinning, wherein the density of the mature silkworms on a spinning plate is 500 heads/m2Checking every 3 hours in the spinning process, and adjusting the density and uniformity of silkworms to obtain flat silks with the thickness of 0.5 mm;
(3) and putting the flat silk into a hot pressing plate for hot pressing. The hot-pressing preheating time is 30s, the hot-pressing time is 8min, the hot-pressing temperature is 60 ℃, and the hot-pressing strength is 5 MPa;
(4) putting the flat plate wires into a ternary solution for pretreatment, wherein the treatment temperature is 40 ℃, and the treatment time is 20 min;
(5) cleaning the pretreated flat wire with deionized water for 3 times, and cleaning with MES for 1 time for later use;
(6) putting the cleaned flat silk into MES solution at a bath ratio of 1:10, adding EDC and NHS, wherein the addition amount of EDC and NHS is 2mg/mL, and then adding epsilon-polylysine, wherein the addition amount of epsilon-polylysine is 10mg/mL, and carrying out shake reaction for 8h at a constant temperature of 25 ℃ to obtain the antibacterial material.
Example 3
A preparation method of a flat wire antibacterial composite material comprises the following steps:
(1) normally feeding the silkworm strain 932-five years old under the conditions of room temperature of 25 ℃ and humidity of 75% -80%, feeding fresh mulberry leaves, and ensuring the illumination period (light/dark): adding fresh folium Mori every 8 hr for 12 hr/12 hr;
(2) placing a plurality of mature silkworms with defecation and urination clustered on a two-dimensional plane for spinning, wherein the density of the mature silkworms on a spinning plate is 500 heads/m2Checking every 3 hours in the spinning process, and adjusting the density and uniformity of silkworms to obtain flat silks with the thickness of 5 mm;
(3) and putting the flat silk into a hot pressing plate for hot pressing. The hot-pressing preheating time is 30s, the hot-pressing time is 10min, the hot-pressing temperature is 150 ℃, and the hot-pressing strength is 15 MPa;
(4) putting the flat plate wires into a ternary solution for pretreatment, wherein the treatment temperature is 60 ℃, and the treatment time is 30 min;
(5) cleaning the pretreated flat wire with deionized water for 3 times, and cleaning with MES for 1 time for later use;
(6) putting the cleaned flat silk into MES solution at a bath ratio of 1:10, adding EDC and NHS, wherein the addition amount of EDC and NHS is 10mg/mL, and then adding epsilon-polylysine, wherein the addition amount of epsilon-polylysine is 80mg/mL, and carrying out shake reaction for 24h at a constant temperature of 60 ℃ to obtain the antibacterial material.
Example 3
A preparation method of a flat wire antibacterial composite material comprises the following steps:
(1) normally feeding the silkworm strain 932-five years old under the conditions of room temperature of 25 ℃ and humidity of 75% -80%, feeding fresh mulberry leaves, and ensuring the illumination period (light/dark): adding fresh folium Mori every 8 hr for 12 hr/12 hr;
(2) placing a plurality of mature silkworms with defecation and urination clustered on a two-dimensional plane for spinning, wherein the density of the mature silkworms on a spinning plate is 500 heads/m2Checking every 3 hours in the spinning process, and adjusting the density and uniformity of silkworms to obtain flat silks with the thickness of 2 mm;
(3) and putting the flat silk into a hot pressing plate for hot pressing. The hot-pressing preheating time is 30s, the hot-pressing time is 2min, the hot-pressing temperature is 80 ℃, and the hot-pressing strength is 9 MPa;
(4) putting the flat wire into a ternary solution for pretreatment, wherein the treatment temperature is 55 ℃, and the treatment time is 18 min;
(5) cleaning the pretreated flat wire with deionized water for 3 times, and cleaning with MES for 1 time for later use;
(6) putting the cleaned flat silk into MES solution at a bath ratio of 1:10, adding EDC and NHS, wherein the addition amount of EDC and NHS is 6mg/mL, and then adding epsilon-polylysine, wherein the addition amount of epsilon-polylysine is 50mg/mL, and carrying out shake reaction for 5h at the constant temperature of 35 ℃ to obtain the antibacterial material.
Test examples
The comparative material was prepared as follows:
(1) normally feeding the silkworm strain 932-five years old under the conditions of room temperature of 25 ℃ and humidity of 75% -80%, feeding fresh mulberry leaves, and ensuring the illumination period (light/dark): adding fresh folium Mori every 8 hr for 12 hr/12 hr;
(2) placing a plurality of mature silkworms with defecation and urination clustered on a two-dimensional plane for spinning, wherein the density of the mature silkworms on a spinning plate is 500 heads/m2Checking every 3 hours in the spinning process, and adjusting the density and uniformity of silkworms to obtain flat silks with the thickness of 0.5 mm;
(3) and putting the flat silk into a hot pressing plate for hot pressing. The hot-pressing preheating time is 30s, the hot-pressing time is 8min, the hot-pressing temperature is 60 ℃, and the hot-pressing strength is 5MPa, so that the comparative material is obtained.
The comparative materials and the 4 antibacterial materials prepared in example 1 were divided into A, B groups under the same conditions for zone experiments, wherein the strain selected in group A was Escherichia coli, and the strain selected in group B was Staphylococcus, and the specific experimental results are shown in FIG. 1.
It is apparent from fig. 1 that the plate yarn without the epsilon-polylysine grafting treatment cannot form a bacteriostatic zone, while the diameter of the bacteriostatic zone of the plate yarn prepared in example 1 gradually increases with the increase of the dosage of the epsilon-polylysine, and the diameter of the bacteriostatic zone increases to the maximum when the dosage of the epsilon-polylysine is 100mg/ml, so that it is apparent that the bacteriostatic material prepared by the invention has excellent antibacterial effect, wherein the antibacterial effect is optimized with the dosage of the epsilon-polylysine being 100 mg/ml.
The comparative material (group A), the antibacterial material containing epsilon-polylysine prepared in example 1 in an amount of 20mg/ml (group B), and the antibacterial material containing epsilon-polylysine prepared in example 1 in an amount of 100mg/ml (group C) were observed by SEM, and the specific results are shown in FIG. 2.
As is apparent from FIG. 2, compared with the comparative material, the filling between fibers of the antibacterial material prepared by the invention is more complete, the surface is smoother, and the filling between fibers is more complete and the surface of the fibers is smoother as the dosage of the epsilon-polylysine is increased although the fiber network structure is not obviously changed.
Meanwhile, the antibacterial material prepared by the invention has no toxicity to cells, and the results show that the antibacterial material has excellent antibacterial capability and is very comfortable to stick to a human body, so that the antibacterial material is very suitable for the field of biomedical materials such as tissue engineering skin, antibacterial dressing and the like.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The antibacterial composite material of the flat plate yarn is characterized by comprising the flat plate yarn and epsilon-polylysine crosslinked on the surface of the flat plate yarn.
2. A method for preparing the flat-wire antibacterial composite material of claim 1, which is characterized by comprising the following steps:
(1) putting the flat plate silk into a ternary solution for surface treatment, and taking out the flat plate silk for later use when the surface of the flat plate silk is slightly dissolved but the complete structure state is kept;
(2) grafting epsilon-polylysine on the surface of the flat silk subjected to the surface treatment in the step 1) through a cross-linking agent to obtain the antibacterial material.
3. The method for preparing the flat wire antibacterial composite material according to claim 2, characterized in that before the surface treatment of the flat wire, the flat wire is subjected to hot pressing treatment, wherein the hot pressing treatment time is 1-10min, the hot pressing temperature is 60-180 ℃, and the hot pressing pressure is 5-15 MPa.
4. The method for preparing the flat-wire antibacterial composite material according to claim 2, wherein the ternary solution is prepared from anhydrous calcium chloride, anhydrous ethanol and water, wherein the weight ratio of the anhydrous calcium chloride: anhydrous ethanol: the molar ratio of water is 1:2: 8.
5. The method for preparing the flat wire antibacterial composite material according to claim 2, wherein the soaking time in the ternary solution is 3-30min and the soaking temperature is 40-60 ℃ during the surface treatment.
6. The method for preparing the flat-wire antibacterial composite material according to claim 2, wherein the cross-linking agent comprises EDC and NHS, and the mass ratio of EDC to NHS is 1: 1.
7. The method for preparing the flat-plate-wire antibacterial composite material according to claim 6, wherein during cross-linking, the flat-plate wire subjected to surface treatment is immersed in MES solution, and then the cross-linking agent and the epsilon-polylysine are added, so that the epsilon-polylysine is cross-linked on the surface of the flat-plate wire.
8. The method for preparing the flat-plate silk antibacterial composite material according to claim 7, wherein the concentration of the MES solution is 0.1mol/ml, the mass ratio of the MES solution to the flat-plate silk is 1:10, the addition amount of EDC and NHS is 2-10mg/ml, and the addition amount of epsilon-polylysine is 10-100 mg/ml.
9. The method for preparing the flat-wire antibacterial composite material according to claim 8, wherein the reaction temperature during crosslinking is 18-60 ℃ and the reaction time is 1-24 hours.
10. The method for preparing flat filament antibacterial composite material according to any of claims 2 to 9, wherein the thickness of the flat filament is 0.5 to 5 mm.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115089765A (en) * | 2022-07-15 | 2022-09-23 | 西南大学 | Flat wire/polylactic acid composite porous bone repair scaffold and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120129255A1 (en) * | 2009-07-21 | 2012-05-24 | Trustees Of Tufts College | Functionalization of silk material by avidin-biotin interaction |
| CN103911857A (en) * | 2014-03-24 | 2014-07-09 | 灵山县桂合丝业有限公司 | Production method of anti-yellow anti-bacterial silk quilt cover |
| CN106668954A (en) * | 2017-02-10 | 2017-05-17 | 烟台正海生物科技股份有限公司 | Antibacterial cation-modified absorbable pachymeninx repair material and preparation method and application thereof |
| CN106757387A (en) * | 2017-01-10 | 2017-05-31 | 南丹县农业局 | The preparation method of golden yellow flat board silk |
| CN110592936A (en) * | 2019-09-19 | 2019-12-20 | 西南大学 | Preparation of anti-ultraviolet silk fabric by using EDC/NHS solution |
-
2021
- 2021-11-12 CN CN202111336285.2A patent/CN114032691A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120129255A1 (en) * | 2009-07-21 | 2012-05-24 | Trustees Of Tufts College | Functionalization of silk material by avidin-biotin interaction |
| CN103911857A (en) * | 2014-03-24 | 2014-07-09 | 灵山县桂合丝业有限公司 | Production method of anti-yellow anti-bacterial silk quilt cover |
| CN106757387A (en) * | 2017-01-10 | 2017-05-31 | 南丹县农业局 | The preparation method of golden yellow flat board silk |
| CN106668954A (en) * | 2017-02-10 | 2017-05-17 | 烟台正海生物科技股份有限公司 | Antibacterial cation-modified absorbable pachymeninx repair material and preparation method and application thereof |
| CN110592936A (en) * | 2019-09-19 | 2019-12-20 | 西南大学 | Preparation of anti-ultraviolet silk fabric by using EDC/NHS solution |
Non-Patent Citations (1)
| Title |
|---|
| 凌敏等: "原生态蚕丝创伤敷料的制备及性能测试", 《蚕业科学》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115089765A (en) * | 2022-07-15 | 2022-09-23 | 西南大学 | Flat wire/polylactic acid composite porous bone repair scaffold and preparation method thereof |
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