CN109180964A - A kind of fibroin albumen photocuring hydrogel and preparation method thereof - Google Patents
A kind of fibroin albumen photocuring hydrogel and preparation method thereof Download PDFInfo
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- CN109180964A CN109180964A CN201811006463.3A CN201811006463A CN109180964A CN 109180964 A CN109180964 A CN 109180964A CN 201811006463 A CN201811006463 A CN 201811006463A CN 109180964 A CN109180964 A CN 109180964A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/03—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in aqueous media
- C08J3/075—Macromolecular gels
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2389/00—Characterised by the use of proteins; Derivatives thereof
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Abstract
The present invention relates to a kind of fibroin albumen photocuring hydrogels and preparation method thereof.It prepares the silk fibroin hydrogel of inierpeneirating network structure by ultraviolet light solidification using fibroin albumen as raw material.It is dissolved in silk fibroin protein solution using monomer N-vinyl pyrrolidones, it polymerize n-vinyl pyrrolidone by ultraviolet light and horseradish peroxidase enzyme catalytic and forms polyvinylpyrrolidone macromolecular and the generation physical entanglement of silk fibroin molecular chain, obtain that a kind of translucency is good, the excellent novel silk fibroin hydrogel of degradation property.
Description
Technical field
The present invention relates to hydrogel material technical fields, in particular to a kind of to pass through the cured novel fibroin albumen of ultraviolet light
Hydrogel and preparation method thereof.
Background technique
Silk is secretion silk liquid concretionary continuous fiber when matured silkworm cocoons.Fibroin is a kind of day derived from silk
Right hmw protein, content account for the 70%~80% of silk, contain 18 kinds of amino acid, and 11 kinds therein are amino needed by human
Acid;On the other hand, fibroin albumen effect harmless to the human body, securely and reliably, have good biocompatibility, be suitable for exploitation at
Functional material.Therefore, right both at home and abroad with going deep into its unique amino acid composition and the Study on Physico-chemical such as crystalline texture
The application of fibroin is just from traditional field of textiles actively to multi-field exploration, application of the fibroin albumen in field of biomedical materials
Also increasingly extensively.
N-vinyl pyrrolidone abbreviation NVP, it medicine, food, cosmetics, adhesive, in terms of suffer from
Extensive purposes.It is polyvinylpyrrolidone that NVP is polymerizable in acid condition or in the presence of initiator.NVP can also and its
Its monomer (such as vinyl acetate cruel, ethylene, acrylonitrile, isobutene vinegar, acrylic acid isopropyl alkene vinegar) copolymerization obtains copolymer.
NVP polymerize to form polyvinylpyrrolidone (polyvinyl pyrrolidone) abbreviation PVP, is a kind of non-ionic macromolecule
Compound.PVP is as a kind of synthesizing water-solubility high-molecular compound, the general aspects with water-soluble high-molecular compound, glue
Body protective effect, film forming, caking property, hygroscopicity, solubilising or cohesion, but its is most characteristic, thus paid attention to by people
Be its excellent solubility property and physiological compatibility.PVP has excellent physiological inertia, is not involved in human metabolism, and have
There is excellent biocompatibility, any stimulation is not formed to skin, mucous membrane, eye etc..Pharmaceutical grade PVP is the international three big medicines advocated
With one of new auxiliary material, the glidant of tablet, the binder of granule, the cosolvent of injection, capsule can be used as;The detoxification of medicament for the eyes
Agent, prolongation of effect agent, lubricant and coating film forming agent, the dispersing agent and enzyme of liquid preparation and the stabilizer of heat-sensitive drug, can be used as
Cryopreservative.Therefore, PVP can be used in biomaterial, but its water solubility limits the application range as implantation material.
Ultraviolet light solidification is generally needed to be added photosensitizer, and photosensitizer residual is likely to cause toxicity.Chinese invention patent
(CN107118359A) the biological photosensitizer riboflavin photocatalysis formation silk fibroin hydrogel of use, but photosensitizer riboflavin
Residual is likely to cause the decline of transparency.Chinese invention patent (CN105294955A) discloses a kind of for many cells sorting
With the photocuring hydrogel and preparation method thereof of stem cell constituency differentiation, it is with the modified polymer material with light-cured performance
Raw material is prepared, but obtained hydrogel elastic modulus is poor.Chinese invention patent (CN106009709A) discloses one kind
Fibroin albumen interpenetration network hydrogel and preparation method thereof passes through horseradish peroxidase and hydrogen peroxide catalyzed N- vinylpyridine
Polymerization reaction occurs for pyrrolidone monomer, generates polyvinylpyrrolidone and molecular entanglement occurs with fibroin albumen macromolecular,
Interpenetrating networks (IPN) hydrogel based on random coil structure is formed under certain condition.Silk fibroin hydrogel material tool
There are high-intensitive, elasticity and transparency.But the silk fibroin hydrogel material being prepared, may tool because joined hydrogen peroxide
There is certain cytotoxicity, certain influence is produced to the research of cell compatibility.
Summary of the invention
The present invention is in view of the deficienciess of the prior art, good, the excellent fibroin albumen of degradation property that provides a kind of translucency
Photocuring hydrogel and preparation method thereof.
Realize that the technical solution of the object of the invention is to provide a kind of preparation method of fibroin albumen photocuring hydrogel, with family
Silk is raw material, through degumming, dissolution, dialysis treatment, obtains silk fibroin water solution, then the following steps are included:
(1) configuration concentration is the horseradish peroxidase aqueous solution of 1000 unit/mL;
(2) concentration for adjusting silk fibroin water solution is 10g/L~100g/L;
(3) n-vinyl pyrrolidone and horseradish peroxidase aqueous solution, N- second are separately added into silk fibroin water solution
Final concentration of 20 g/L~100g/ of vinyl pyrrolidone, final concentration of 10unit/mL~50 of horseradish peroxidase
Unit/mL obtains composite solution after mixing;
(4) composite solution is poured into the transparent mould of permeable ultraviolet light, oxygen is passed through into composite solution, kept compound
Oxygen partial pressure is in a saturated state in solution;
(5) min of 5min~40 is handled under the conditions of room temperature, ultraviolet light, obtains a kind of fibroin albumen photocuring hydrogel.
Composite solution with a thickness of 5 millimeters~50 millimeters in step (4) mold.
The wavelength of ultraviolet light is 340~400nm in step (5), and intensity is 15mW~65mW;The distance of ultraviolet light is
5cm~10cm.
Technical solution of the present invention further includes a kind of fibroin albumen photocuring hydrogel that the method that is prepared as described above obtains.
The present invention is combined together the two by polymerization, to obtain using the biocompatibility of both fibroin albumen and PVP
The hydrogel material of two kinds of macromolecule advantages must be integrated.Meanwhile influence of the initiator for biocompatibility in order to prevent, this hair
It is bright that photocuring system has been selected to prepare composite hydrogel.It is molten that the present invention uses monomer N-vinyl pyrrolidones to be dissolved in fibroin albumen
In liquid, n-vinyl pyrrolidone formation polyvinylpyrrolidone is polymerize by ultraviolet light and horseradish peroxidase enzyme catalytic and is divided greatly
Son generates physical entanglement with silk fibroin molecular chain, obtains a kind of novel silk fibroin hydrogel.
The principle of the present invention is: by natural polymer fibroin albumen and n-vinyl pyrrolidone in horseradish peroxidating
Interpenetrating networks silk fibroin hydrogel is prepared using light polymerization process under object enzyme effect.Oxygen energy, shape are improved under ultraviolet lighting
At ozone, super oxygen, the upper state oxygen such as peroxide, drop is reacted with water can form relatively stable hydrogen peroxide.Horseradish peroxidase
Catalyzing hydrogen peroxide, which forms hydroxyl free radical and then causes N- vinylpyrrolidone, occurs polymerization reaction, the polymer and silk of generation
Fibroin macromolecular generates physical entanglement to which the inierpeneirating network structure hydrogel of homogeneous transparent be prepared.
Compared with prior art, the invention has the following advantages that
1. SF/NVP hydrogel provided by the invention is not directly added into hydrogen peroxide during the preparation process, the micro- of intermediate formation is reacted
Amount hydrogen peroxide is catalytically decomposed rapidly, does not remain, so the hydrogel formed does not have residual toxicity, is able to maintain good life
Object compatibility.
2. SF/NVP hydrogel through performance provided by the invention reaches intimate 100%, it is catalyzed to be formed relative to photosensitizer
SF hydrogel does not have in SF/NVP hydrogel photosensitizer to interfere its light transmission, and toxicity caused by remaining without photosensitizer,
It is a kind of more preferably Contact Lens.
Detailed description of the invention
Fig. 1 is N- vinylpyrrolidone/silk fibroin hydrogel provided in an embodiment of the present invention and pure silk hydrogel
Electromicroscopic photograph comparison diagram, wherein A is pure SF hydrogel, and B is N- vinylpyrrolidone/fibroin albumen (SF/NVP) photocuring water
Gel.
Specific embodiment
In the following with reference to the drawings and specific embodiments, technical solution that the present invention is further explained.
Embodiment one
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000 unit/mL horseradish peroxidase aqueous solutions, and adjusting fibroin albumen concentration is 10 g/
N-vinyl pyrrolidone is added in L, makes 30 g/L of its concentration, and horseradish peroxidase aqueous solution is added, makes its concentration 10
unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 20 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 30 min of ultraviolet light, a length of 340~400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 40 mW, the irradiation distance of ultraviolet light is 6cm.Then it is removed from the molds, obtains a kind of photocuring silk fibroin hydrogel.
Referring to attached drawing 1, it is N- vinylpyrrolidone/silk fibroin hydrogel provided in this embodiment and pure silk element water-setting
The electromicroscopic photograph comparison diagram of glue, wherein A figure is pure SF hydrogel, and B figure is SF/NVP photocuring hydrogel.
Be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample, in TMS-
Compressive Mechanical test is carried out on PRO type Texture instrument, test result is referring to table 1.
Embodiment two
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000 unit/mL horseradish peroxidase aqueous solutions, and adjusting fibroin albumen concentration is 20g/
N-vinyl pyrrolidone is added in L, makes its concentration 30g/L, and horseradish peroxidase aqueous solution is added, makes its concentration 20
unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the transparent mould of permeable ultraviolet light, is made molten in mold
Liquid is with a thickness of 20 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 25 min of ultraviolet light, a length of 340~400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 30 mW, the irradiation distance of ultraviolet light is 7 cm.Then it is removed from the molds, obtains a kind of photocuring silk fibroin hydrogel.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Embodiment three
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000 unit/mL horseradish peroxidase aqueous solutions, and adjusting fibroin albumen concentration is 30 g/
N-vinyl pyrrolidone is added in L, makes 40 g/L of its concentration, and horseradish peroxidase aqueous solution is added, makes its concentration 30
unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 20 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 20 min of ultraviolet light, a length of 340-400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 60 mW, the irradiation distance of ultraviolet light is 8 cm.Then it is removed from the molds, obtains a kind of photocuring silk fibroin hydrogel.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Example IV
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000 unit/mL horseradish peroxidase aqueous solutions, and adjusting fibroin albumen concentration is 40g/
N-vinyl pyrrolidone is added in L, makes its concentration 30g/L, and horseradish peroxidase aqueous solution is added, makes its concentration
40unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 20 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 35 min of ultraviolet light, a length of 340-400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 37 mW, the irradiation distance of ultraviolet light is 8 cm.Then it is removed from the molds, obtains a kind of photocuring silk fibroin hydrogel.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Embodiment five
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000 unit/mL horseradish peroxidase aqueous solutions, and adjusting fibroin albumen concentration is 50g/
N-vinyl pyrrolidone is added in L, makes its concentration 30g/L, and horseradish peroxidase aqueous solution is added, makes its concentration 50
unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 20 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 38 min of ultraviolet light, a length of 340-400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 43 mW, the irradiation distance of ultraviolet light is 8.5 cm.Then it is removed from the molds, obtains a kind of photocuring fibroin albumen water-setting
Glue.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Embodiment six
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000 unit/mL horseradish peroxidase aqueous solutions, and adjusting fibroin albumen concentration is 60 g/
N-vinyl pyrrolidone is added in L, makes 70 g/L of its concentration, and horseradish peroxidase aqueous solution is added, makes its concentration 50
unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 30 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 10 min of ultraviolet light, a length of 340-400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 30 mW, the irradiation distance of ultraviolet light is 5 cm.Then it is removed from the molds, obtains a kind of photocuring silk fibroin hydrogel.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Embodiment seven
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000unit/mL horseradish peroxidase aqueous solution, and adjusting fibroin albumen concentration is 70g/L,
N-vinyl pyrrolidone is added, makes its concentration 30g/L, horseradish peroxidase aqueous solution is added, makes its concentration
50unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 40 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 30 min of ultraviolet light, a length of 340-400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 43 mW, the irradiation distance of ultraviolet light is 7.5 cm.Then it is removed from the molds, obtains a kind of photocuring fibroin albumen water-setting
Glue.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Embodiment eight
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000unit/mL horseradish peroxidase aqueous solution, and adjusting fibroin albumen concentration is 80g/L,
N-vinyl pyrrolidone is added, makes its concentration 20g/L, horseradish peroxidase aqueous solution is added, makes its concentration
50unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 50 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) at room temperature with 43 min of ultraviolet light, a length of 340-400nm of ultraviolet light wave, the exposure intensity of ultraviolet light
For 45 mW, the irradiation distance of ultraviolet light is 8.1 cm.Then it is removed from the molds, obtains a kind of photocuring fibroin albumen water-setting
Glue.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Embodiment nine
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000 unit/mL horseradish peroxidase aqueous solutions, and adjusting fibroin albumen concentration is 80 g/
N-vinyl pyrrolidone is added in L, makes 30 g/L of its concentration, and horseradish peroxidase aqueous solution is added, makes its concentration 50
unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 40 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) it is then removed from the molds with 30 min of ultraviolet light at room temperature, obtains a kind of photocuring fibroin albumen
Hydrogel.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
Embodiment ten
(1) preparation of silk fibroin water solution: 3g anhydrous Na HCO is weighed3With 1g anhydrous Na2CO3It is put into the 4L deionization boiled
In water, 80g silk cocoon is added after completely dissolution, adjust solution state be it is slightly boiled, stirred every 10 minutes with glass bar it is primary, 30 points
It is washed with deionized after clock completely, repeats aforesaid operations 3 times, weigh new anhydrous Na HCO every time3And anhydrous Na2CO3;Sufficiently
After cleaning, by silk garnetting, it is put into 60 DEG C of baking ovens and dries.The lithium-bromide solution of the 9.3mol/L of 100ml is taken to pour into conical flask
In, it is heated to 65 DEG C in constant temperature blender with magnetic force, the degumming fibroin of gross weight 15g is added several times, is dissolved at 65 ± 2 DEG C
30~40 minutes, taking-up, which is fitted into bag filter, after cooling sealed, and is placed in deionized water and dialyses 3~4 days under low temperature, dialysis is completed
Afterwards, it will obtain being fitted into reagent bottle after silk fibroin protein solution is filtered with absorbent cotton, cryo-conservation is spare.
(2) configuration concentration is 1000unit/mL horseradish peroxidase aqueous solution, and adjusting fibroin albumen concentration is 51g/L,
N-vinyl pyrrolidone is added, makes its concentration 50g/L, horseradish peroxidase aqueous solution is added, makes its concentration 50
unit/mL。
(3) above-mentioned uniformly mixed composite solution is added in the mold of UV transparent, makes sample path length in mold
It is 30 millimeters.
(4) it is constantly passed through oxygen in the solution, keeps oxygen partial pressure in solution in a saturated state.
(5) it is then removed from the molds with 30 min of ultraviolet light at room temperature, obtains a kind of photocuring fibroin albumen
Hydrogel.
(6) be made into perforating mold having a size of 10 mm(diameters) × 8 mm(high) cylindrical type gel sample,
Compressive Mechanical test is carried out on TMS-PRO type Texture instrument, test result is referring to table 1.
The mechanical property of 1 photocuring hydrogel of table
Sample | Compression ratio (%) | Compressive strength (kPa) | Compression ratio (%) | Compression resilience (%) |
Pure silk hydrogel | 50 | 11.2 | 50 | 13.9 |
Embodiment 1 | 90 | 15.6 | 80 | 79 |
Embodiment 2 | 90 | 20.1 | 80 | 81 |
Embodiment 3 | 90 | 26.7 | 80 | 81.2 |
Embodiment 4 | 90 | 37.9 | 80 | 87 |
Embodiment 5 | 90 | 47.5 | 80 | 86.9 |
Embodiment 6 | 90 | 55.3 | 80 | 87.8 |
Embodiment 7 | 90 | 60.9 | 80 | 93.9 |
Embodiment 8 | 90 | 61.9 | 80 | 94 |
Embodiment 9 | 90 | 63.8 | 80 | 87.6 |
Embodiment 10 | 90 | 80.1 | 80 | 80.8 |
As it can be seen from table 1 the compressive strength of SF/NVP hydrogel can reach 60kpa or more when compression ratio is 90%,
And the compressive strength of pure silk hydrogel is only 11.2kpa, when compression ratio is 80%, SF/NVP hydrogel compression resilience can
Up to 93%, far superior to the 13.9% of pure silk hydrogel.
Claims (4)
1. a kind of preparation method of fibroin albumen photocuring hydrogel, using domestic silkworm silk as raw material, through degumming, dissolution, dialysis treatment,
Obtain silk fibroin water solution, it is characterised in that again the following steps are included:
(1) configuration concentration is the horseradish peroxidase aqueous solution of 1000 unit/mL;
(2) concentration for adjusting silk fibroin water solution is 10g/L~100g/L;
(3) n-vinyl pyrrolidone and horseradish peroxidase aqueous solution, N- second are separately added into silk fibroin water solution
Final concentration of 20 g/L~100g/ of vinyl pyrrolidone, final concentration of 10unit/mL~50 of horseradish peroxidase
Unit/mL obtains composite solution after mixing;
(4) composite solution is poured into the transparent mould of permeable ultraviolet light, oxygen is passed through into composite solution, kept compound
Oxygen partial pressure is in a saturated state in solution;
(5) min of 5min~40 is handled under the conditions of room temperature, ultraviolet light, obtains a kind of fibroin albumen photocuring hydrogel.
2. a kind of preparation method of fibroin albumen photocuring hydrogel according to claim 1, it is characterised in that: step
(4) in mold composite solution with a thickness of 5 millimeters~50 millimeters.
3. a kind of preparation method of fibroin albumen photocuring hydrogel according to claim 1, it is characterised in that: step
(5) wavelength of ultraviolet light is 340~400nm in, and intensity is 15mW~65mW;The distance of ultraviolet light is 5cm~10cm.
4. a kind of fibroin albumen photocuring hydrogel obtained by claim 1 preparation method.
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CN110229530A (en) * | 2019-07-05 | 2019-09-13 | 青岛大学 | A kind of dual network silk fibroin hydrogel and preparation method thereof |
CN116655945A (en) * | 2023-02-03 | 2023-08-29 | 媄典(北京)医疗器械有限公司 | Photo-curing silk fibroin hydrogel and preparation method thereof |
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CN106009709A (en) * | 2016-06-25 | 2016-10-12 | 南通纺织丝绸产业技术研究院 | Silk fibroin hydrogel adopting IPN (interpenetrating polymer network) structure and preparation method of silk fibroin hydrogel |
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CN110229530B (en) * | 2019-07-05 | 2021-11-19 | 青岛大学 | Double-network silk fibroin hydrogel and preparation method thereof |
CN116655945A (en) * | 2023-02-03 | 2023-08-29 | 媄典(北京)医疗器械有限公司 | Photo-curing silk fibroin hydrogel and preparation method thereof |
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